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Transcript of ars.els-cdn.com · Web viewSupplementary Material. Highly selective extraction of uranium from...
Supplementary Material
Highly selective extraction of uranium from
nitric acid medium with phosphine oxide
functionalized pillar[5]arenes in room
temperature ionic liquid
Lixi Chen Ying Wang Xiangyang Yuan Yi Ren Ning Liu Lihua Yuan and Wen Feng
Institute of Nuclear Science and Technology Key Laboratory for Radiation
Physics and Technology of Ministry of Education College of Chemistry Sichuan
University Chengdu 610064 China
Fig S1 Partial 2D NOESY spectrum (400 MHz chloroform-d6 298 K mixing time
= 03 s) of L-I (150 mM) and C8minNTf2 (150 mM)
Fig S2 UV-vis spectrophotometric titration of L-I (10 times 10-4 M) with C8minNTf2 (0-
50 equiv) in CHCl3 at 298 K
Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2
(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm
Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the
absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times
10-3 M
Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I
and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer
simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+
(d) computer simulation of [L-I sup C8mim]+
Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model
of L-I The structure L-I was optimized by the density functional theory (DFT)
method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S1 Partial 2D NOESY spectrum (400 MHz chloroform-d6 298 K mixing time
= 03 s) of L-I (150 mM) and C8minNTf2 (150 mM)
Fig S2 UV-vis spectrophotometric titration of L-I (10 times 10-4 M) with C8minNTf2 (0-
50 equiv) in CHCl3 at 298 K
Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2
(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm
Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the
absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times
10-3 M
Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I
and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer
simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+
(d) computer simulation of [L-I sup C8mim]+
Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model
of L-I The structure L-I was optimized by the density functional theory (DFT)
method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S2 UV-vis spectrophotometric titration of L-I (10 times 10-4 M) with C8minNTf2 (0-
50 equiv) in CHCl3 at 298 K
Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2
(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm
Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the
absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times
10-3 M
Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I
and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer
simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+
(d) computer simulation of [L-I sup C8mim]+
Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model
of L-I The structure L-I was optimized by the density functional theory (DFT)
method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2
(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm
Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the
absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times
10-3 M
Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I
and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer
simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+
(d) computer simulation of [L-I sup C8mim]+
Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model
of L-I The structure L-I was optimized by the density functional theory (DFT)
method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the
absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times
10-3 M
Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I
and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer
simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+
(d) computer simulation of [L-I sup C8mim]+
Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model
of L-I The structure L-I was optimized by the density functional theory (DFT)
method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I
and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer
simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+
(d) computer simulation of [L-I sup C8mim]+
Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model
of L-I The structure L-I was optimized by the density functional theory (DFT)
method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model
of L-I The structure L-I was optimized by the density functional theory (DFT)
method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+
C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue
= N) All terminal phenyl groups of each chain in the host molecule are replaced by
methyl groups for simplicity and hydrogens except the ones involved in hydrogen
bonding between host and guest are omitted for clarity The dashed pink lines in (b)
indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring
(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =
3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange
lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =
4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =
3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was
optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)
level by employing the Gaussian 09 program [1]
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and
UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result
based on the absorbance at 259 nm
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O
(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The
total concentration is 10 times 10-4 M
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest
complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O
and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)
basis set has been used for light atoms (H C O and P) while the relativistic atomic
natural orbital (ANO) has been employed for uranium as reported [2] All terminal
phenyl groups of each chain in the host molecule L-I are replaced by methyl groups
for simplicity The dashed cyan lines in (b) indicate the coordination distances and
angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =
2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with
L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01
M
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S16 Dependency of UO22+ extraction percentage () on NTf2
- concentration in
the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5
times 10-4 M [HNO3] = 01 M
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5
times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+
Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M
in total) at 10 M HNO3
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
The structure L-I was optimized by the density functional theory (DFT) method at the
B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]
Table S1 Atomic coordinates for the optimized structure of L-I
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 00197870 -43323960 02559940
2 C 12205250 -41410940 -04459780
3 C 11868990 -37634610 -17918270
4 C -00166870 -35643790 -24733650
5 C -12173790 -37661360 -17742800
6 C -11837820 -41458110 -04290290
7 C 00030500 -46867650 17343950
8 C -00002810 -30968900 -39199560
9 O -23917240 -35743320 -24761350
10 O 23948890 -43444920 02524550
11 C -36055940 -38742020 -17934450
12 C -47771560 -36604000 -27451190
13 P -63445210 -42232170 -19580650
14 C 36088510 -42412490 -04859000
15 C 47805280 -45527850 04382430
16 P 63497370 -46135900 -05242480
17 C -76805060 -35566480 -30014400
18 C 76835320 -45847660 07158560
19 C 00168870 -15814840 -40403960
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
20 C 12178010 -08549970 -40739910
21 C 11844180 05416310 -41324020
22 C -00190360 12515170 -41558730
23 C -12199100 05245210 -41327500
24 C -11865250 -08721680 -40769380
25 C -00020840 27717930 -41598980
26 O -23944170 12509230 -41698100
27 O 23920200 -15823970 -40491290
28 C -36078230 05077820 -42402770
29 C -47804710 14777060 -43294150
30 P -63484820 05531130 -46108440
31 C 36058980 -08485760 -41815890
32 C 47775550 -18237960 -41917010
33 P 63449460 -09291300 -45594340
34 C -76843230 17500020 -42936940
35 C 76811310 -20967310 -41481460
36 C 00186230 -10956650 41982310
37 C 12201550 -17037480 38009920
38 C 11880360 -28677230 30268720
39 C -00148030 -34553310 26260080
40 C -12162760 -28538150 30332150
41 C -11841480 -16910960 38090810
42 C 00003100 02018460 49905010
43 O -23900670 -34635170 26344910
44 O 23936780 -11011410 42109710
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
45 C -36043440 -29056590 31283220
46 C -47755950 -37457110 26317830
47 P -63437250 -31682990 34067110
48 C 36083190 -17710120 38864630
49 C 47791010 -09884940 44703490
50 P 63473010 -19260690 42362710
51 C -76795240 -39530870 24489320
52 C 76827130 -07390570 45904000
53 C 00153410 33556780 -27561450
54 C 12165320 36119400 -20759170
55 C 11836990 40976840 -07652240
56 C -00194570 43394490 -00969410
57 C -12206460 40939800 -07810200
58 C -11878340 36101060 -20924870
59 C -00018180 48101950 13485630
60 O -23943880 43539680 -01004320
61 O 23907010 33638520 -27602520
62 C -36091040 41940540 -08272740
63 C -47793740 45800050 00701650
64 P -63488730 45702540 -08936140
65 C 36047100 37155260 -21029130
66 C 47764730 34260850 -30340730
67 P 63449530 40433850 -22914950
68 C -76822130 46425430 03451750
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
69 C 76796270 32941360 -32789030
70 C 00162150 36537010 23352700
71 C 12175990 30874110 27904030
72 C 11850630 19917040 36583810
73 C -00178650 14292140 40934110
74 C -12193050 20016840 36461160
75 C -11867550 30993240 27805970
76 O -23931770 14329110 41011110
77 O 23915570 36626210 23435210
78 C -36074550 20760760 37250640
79 C -47789070 13420670 43677120
80 P -63457070 22623430 40653280
81 C 36057100 31487260 28832640
82 C 47774370 39432930 23177050
83 P 63447980 34322720 31397500
84 C -76831460 11071770 45064180
85 C 76818430 41294980 21181620
86 H 21013780 -35809300 -23403700
87 H -20980890 -42749440 01347560
88 H 08866900 -52847520 19723740
89 H -08799460 -52964110 19435320
90 H 08826990 -35085390 -44159290
91 H -08839140 -34838910 -44342640
92 H -35742700 -49153880 -14402480
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
93 H -37233920 -32316120 -09140440
94 H -46161360 -42114870 -36790820
95 H -49016470 -26016250 -29974060
96 H 35797480 -49449470 -13308140
97 H 37243230 -32337850 -09005200
98 H 46225570 -55118920 09452930
99 H 49004430 -37823160 12077990
100 H -76434870 -39943350 -40042500
101 H -75597060 -24730230 -30908310
102 H -86431070 -37964500 -25410480
103 H 86469460 -45456810 01997290
104 H 75585520 -37074320 13572870
105 H 76483200 -54816520 13426360
106 H 20988910 11197140 -41280460
107 H -21011790 -14478830 -40272330
108 H -08854910 31411920 -46873370
109 H 08811670 31154970 -47047450
110 H -35780570 -01515320 -51201970
111 H -37228600 -01286550 -33560360
112 H -46238170 21930400 -51453150
113 H -49007600 20480010 -34018110
114 H 35757330 -02643620 -51130540
115 H 37221500 -01411830 -33531900
116 H 46159270 -26065640 -49421050
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
117 H 49018910 -23121250 -32189570
118 H -86466660 12366910 -43743490
119 H -75593970 21712700 -32918820
120 H -76516670 25676000 -50209520
121 H 86436070 -15937430 -42775160
122 H 75610800 -24303490 -31132440
123 H 76437470 -29736710 -48024620
124 H 21032460 -33329090 26855320
125 H -20992450 -11959830 41055960
126 H -08830800 02122900 56343980
127 H 08835530 02448410 56332290
128 H -37215030 -18715500 27861590
129 H -35741560 -28884940 42277170
130 H -48987580 -36613230 15464600
131 H -46150000 -48036940 28701940
132 H 35787520 -27919890 42945260
133 H 37257020 -18538460 28004110
134 H 46187940 -08012950 55385990
135 H 49016970 -00192220 39746850
136 H -76441030 -50421520 25546390
137 H -75572680 -37027360 13910760
138 H -86420140 -35881380 28184560
139 H 86455540 -12205450 43975780
140 H 75605600 01396900 39504370
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
141 H 76461250 -04153020 56355440
142 H 20983550 42703960 -02138010
143 H -21026550 33853950 -26245840
144 H 08814340 54342930 15081110
145 H -08851770 54254960 15386850
146 H -37264890 31569980 -11602990
147 H -35797060 48281970 -17255700
148 H -49008730 38724970 08977400
149 H -46183110 55752260 05008530
150 H 35744440 47813370 -18328320
151 H 37214620 31440920 -11755340
152 H 46175070 39035460 -40080730
153 H 48983660 23506300 -32035770
154 H -86457820 45654330 -01663730
155 H -75594510 38181730 10537050
156 H -76447190 55856630 08997720
157 H 86426430 35676380 -28385570
158 H 75568770 22070910 -32823760
159 H 76435620 36515110 -43130950
160 H 20999720 15230270 39956620
161 H -21017010 35346680 24012850
162 H -35773080 31258160 40521740
163 H -37247030 20741310 26358330
164 H -46171740 12355000 54468020
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
165 H -49038730 03384150 39466760
166 H 35752590 32252350 39800700
167 H 37233130 20893140 26303770
168 H 46174900 50177090 24660340
169 H 49006890 37672690 12434390
170 H -86451200 15748720 42785030
171 H -75630000 01831290 39334340
172 H -76470180 08614090 55725870
173 H 86437880 37974710 25188010
174 H 75603090 37883990 10858800
175 H 76471400 52236570 21286980
176 O -64269380 -16613810 35044770
177 O -64293360 -38521810 -04943380
178 O -64270430 -07232240 -38032640
179 O -64344170 34093180 -18591090
180 O -64278780 28327560 26670580
181 C -63972220 -60407510 -22227520
182 C -64006580 -39799550 50541830
183 C -63999430 35676320 53573370
184 C -64055040 61961060 -17478930
185 C -64115670 02407970 -64205420
186 H -73385460 -64295000 -18244510
187 H -63260250 -62973240 -32837710
188 H -55746040 -65178860 -16837340
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
189 H -73428540 -37199300 55446070
190 H -63303210 -50685010 49716960
191 H -55790450 -36148060 56758530
192 H -73398400 41188950 52649850
193 H -63324760 31438620 63635820
194 H -55753370 42697720 52092640
195 H -73475220 62748580 -22976720
196 H -63349100 70277760 -10407050
197 H -55837250 62665590 -24652620
198 H -73534970 -02600360 -66609560
199 H -63455280 11700970 -69939900
200 H -55895390 -04181110 -67120880
201 O 64301200 -25980610 28839220
202 O 64311520 -35317050 -15778830
203 O 64294170 04113840 -38643350
204 O 64252960 19392080 33669930
205 O 64276530 37865630 -08033690
206 C 64039010 -31320370 56214440
207 C 64117820 -63010540 -12486040
208 C 63985100 -07724950 -63893110
209 C 64040880 58348100 -26958080
210 C 64029850 43832460 47108250
211 H 55799530 40758430 53612130
212 H 73440670 41640720 52228350
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
213 H 63357190 54607240 45340000
214 H 55832520 63551560 -21954380
215 H 73468660 62496370 -23284630
216 H 63337950 60090670 -37734800
217 H 55761200 -01386270 -67310080
218 H 73400730 -02963760 -66767300
219 H 63271100 -17470400 -68811150
220 H 55898290 -64305440 -19574770
221 H 73537650 -64189340 -17914010
222 H 63449240 -70750550 -04783760
223 H 55800580 -38441900 55264580
224 H 73444080 -36875440 55695870
225 H 63363040 -26348600 65935320
The total electronic energy is calculated to be -784883371230 au
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
The complex structure L-I sup C2mim+ was optimized by the density functional theory
(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09
program[1]
Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+
Center
number
Symbol Coordinates (Angstroms)
X Y Z
1 C 02756350 -05968500 42466050
2 C 14943700 -12276390 39439750
3 C 14903900 -24879470 33353620
4 C 03039980 -31549450 30135990
5 C -09139860 -25259580 33228950
6 C -09108470 -12637940 39282840
7 C 02232320 07832490 48832650
8 C 03630630 -45107590 23226290
9 O -20786090 -32040020 30063050
10 O 26465060 -05533880 42778630
11 C -32930310 -26373430 34939270
12 C -44598680 -35422400 31213130
13 P -60563790 -27791560 36422490
14 C 38827850 -12478390 40926180
15 C 50299590 -03708990 45771900
16 P 66180370 -13013600 44403700
17 C -73459900 -37821470 28385260
18 C 79326970 -00515940 45858410
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
19 C 03936780 -43870900 08079520
20 C 15935030 -41726210 01071830
21 C 15606510 -39583140 -12752370
22 C 03656970 -39666250 -19997740
23 C -08266020 -42308680 -13081810
24 C -07972160 -44408170 00762320
25 C 03782950 -36516840 -34873910
26 O -19929420 -42374930 -20541890
27 O 27588210 -41888090 08373520
28 C -31839550 -46534240 -13981300
29 C -43680670 -44395900 -23344230
30 P -59537860 -45830790 -14073460
31 C 39826480 -41737440 00949290
32 C 51573050 -43737580 10431300
33 P 67159460 -45011290 00626610
34 C -72555740 -41025390 -25815790
35 C 80698220 -42788610 12579670
36 C 01699130 39117250 18511990
37 C 13843530 33935450 23334030
38 C 13696580 23987390 33177480
39 C 01782900 19018440 38542890
40 C -10338080 24413970 33937070
41 C -10212550 34335260 24063690
42 C 01249060 49286700 07222230
43 O -21992030 19442680 39488490
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
44 O 25423710 39094770 17998230
45 C -34082410 26009940 35861660
46 C -45845350 19125840 42659800
47 P -61659490 27096230 37497670
48 C 37712880 35065540 24132450
49 C 49263000 42771640 17879540
50 P 64906970 38558960 26721030
51 C -74742310 15571220 42724060
52 C 78374530 44347270 15939080
53 C 03441100 -21565860 -37665030
54 C 15257200 -14052710 -38919410
55 C 14521780 -00264760 -41216640
56 C 02293610 06396460 -42376710
57 C -09504690 -01129330 -41201250
58 C -08804740 -14901860 -38834960
59 C 01976370 21447240 -44564080
60 O -21405630 05765560 -42567650
61 O 27155520 -20881890 -37824670
62 C -33421000 -01855600 -42730910
63 C -45090310 07615720 -45261350
64 P -61146420 -01416750 -44938080
65 C 39127750 -13475640 -40345380
66 C 51139850 -22784360 -39349320
67 P 66465190 -13478350 -43720710
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
68 C -73878400 11607620 -44738510
69 C 80305550 -23762850 -37913740
70 C 01860590 29201620 -31494080
71 C 13810510 32882310 -25024120
72 C 13306770 39465490 -12697820
73 C 01179620 42625500 -06454710
74 C -10701430 39074940 -13006920
75 C -10235580 32485310 -25340530
76 O -22713530 41940730 -06561380
77 O 25556670 29719050 -31399560
78 C -34213560 43775420 -14889300
79 C -45800430 48528680 -06195660
80 P -61873980 46837780 -15107420
81 C 37653550 34677540 -25570460
82 C 49448860 30979590 -34465600
83 P 64845740 38524480 -27627510
84 C -74530690 49494290 -02276110
85 C 78619480 29999430 -35908920
86 H 24186840 -29773430 30738360
87 H -18381000 -07572230 41621930
88 H 11044280 09190170 55151170
89 H -06598560 08460900 55237680
90 H 12584330 -50388540 26609210
91 H -05065850 -51042740 26160380
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
92 H -32258670 -25149180 45842460
93 H -34537930 -16463630 30558300
94 H -43509890 -45344210 35736980
95 H -45206800 -36710730 20350970
96 H 38481460 -21939050 46508630
97 H 40291880 -14912480 30351370
98 H 48678350 -00582700 56150070
99 H 51313730 05309380 39633070
100 H -72888330 -48261790 31620800
101 H -71967490 -37308970 17557930
102 H -83286440 -33804300 31005030
103 H 89016630 -05375450 44413490
104 H 77771640 07227750 38292570
105 H 79118450 04183770 55742370
106 H 24690560 -37466240 -18231850
107 H -17066210 -46367070 06302130
108 H -04836190 -41240820 -39641210
109 H 12812280 -40763930 -39329570
110 H -30957100 -57075120 -10973640
111 H -33490910 -40654990 -04898150
112 H -43445610 -51282910 -31856550
113 H -43483820 -34163590 -27266050
114 H 39489960 -49732370 -06577570
115 H 40960910 -32226490 -04356750
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
116 H 50195830 -52805190 16431340
117 H 52745310 -35274300 17289300
118 H -82292180 -41915960 -20915130
119 H -70893260 -30629370 -28844250
120 H -72410830 -47505370 -34636470
121 H 90212750 -42730790 07189700
122 H 79255030 -33343280 17898500
123 H 80775710 -50923760 19903270
124 H 22928530 19641810 36774780
125 H -19442220 38573720 20326600
126 H -07720200 55437710 08299450
127 H 09947360 55868350 07907440
128 H -35557720 25642270 25012440
129 H -33510820 36611750 38725890
130 H -46465640 08612130 39619670
131 H -44833020 19425610 53565880
132 H 37096030 37018150 34927440
133 H 39303910 24315320 22790230
134 H 47460280 53567480 18435240
135 H 50673180 40103030 07346830
136 H -74838480 14553630 53623080
137 H -72870930 05751250 38259280
138 H -84434880 19416230 39431620
139 H 87945840 41433950 20353900
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
140 H 77212970 39862590 06033410
141 H 78081250 55238980 14890880
142 H 23508680 05703890 -41982360
143 H -17811230 -20813680 -37746510
144 H 10746350 24363580 -50393430
145 H -06914060 24066570 -50353640
146 H -34846790 -07026420 -33165700
147 H -32848820 -09514160 -50597440
148 H -45610210 15267760 -37435370
149 H -43863170 12793300 -54840370
150 H 38484380 -08957180 -50344100
151 H 40189110 -05346960 -33086060
152 H 49938220 -31392890 -46024850
153 H 52460150 -26562410 -29148880
154 H -83736720 06935950 -43977690
155 H -72258290 18255460 -36195660
156 H -73458900 17528350 -53934900
157 H 89667890 -18356830 -39560700
158 H 78958880 -25910470 -27273120
159 H 80640990 -33242280 -43377500
160 H 22394340 42110700 -07465230
161 H -19360190 29525980 -30371530
162 H -31870390 50992470 -22824530
163 H -37023050 34342120 -19706100
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
164 H -44298170 58819900 -02760190
165 H -46686140 42210220 02722560
166 H 36849600 45580840 -24461930
167 H 39096090 30417150 -15588040
168 H 47808770 34471650 -44723060
169 H 51021320 20140180 -34785510
170 H -84444510 48057660 -06660380
171 H -72988630 42330040 05858570
172 H -73871390 59644290 01768210
173 H 88046120 33537550 -31641530
174 H 77570970 19211250 -34446380
175 H 78551510 32078420 -46655560
176 O -61671460 30488890 22690750
177 O -61170760 -12993940 33145330
178 O -59125970 -37581740 -01314420
179 O -61828850 -11273520 -33437550
180 O -62783850 33551620 -22352030
181 C -62182110 -31188290 54360240
182 C -63608330 41927420 48065300
183 C -63106410 61197860 -26389170
184 C -62713230 -09487530 -61320330
185 C -62068680 -63680700 -10869900
186 H -71883810 -27519960 57819850
187 H -61469280 -41892140 56493280
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
188 H -54353360 -25921930 59876600
189 H -73158100 46717750 45741460
190 H -63427400 39335360 58689120
191 H -55592960 49060760 45985170
192 H -72833260 60981990 -31377450
193 H -62088640 70658240 -20994740
194 H -55323030 60572530 -34038180
195 H -72432900 -14460890 -61916880
196 H -61940380 -02232300 -69468390
197 H -54910020 -17045950 -62521660
198 H -71739360 -65091360 -05967110
199 H -61931930 -69464220 -20153490
200 H -54256160 -67421280 -04205820
201 O 65495870 23912860 30475030
202 O 66695930 -21470930 31865480
203 O 67264900 -35427780 -11085200
204 O 65107950 38028240 -12505700
205 O 66211550 00648630 -38298380
206 C 65381490 49616860 41366990
207 C 67347390 -23035720 59731790
208 C 68220670 -62563000 -04639460
209 C 67443000 -13975150 -62040710
210 C 65208090 55680450 -34143390
211 H 56784500 61382390 -30139450
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
212 H 74459010 60510510 -30878670
213 H 64780040 55852580 -45072760
214 H 58973390 -08584440 -66366220
215 H 76646800 -09010440 -65236120
216 H 67456890 -24243700 -65811810
217 H 59933410 -64947540 -11358460
218 H 77576240 -64059170 -10099350
219 H 67971400 -69379340 03911760
220 H 59249660 -30373470 60020840
221 H 76853430 -28439200 59710740
222 H 66833970 -16782620 68692320
223 H 57083510 47263830 48083850
224 H 74734370 47935150 46776760
225 H 64786350 60157530 38500210
226 C -30556520 09069660 -00297450
227 N -42262150 02536320 -00588770
228 C -39715600 -11026370 -00134740
229 C -26138090 -12519110 00456090
230 N -20613390 00112950 00341620
231 C -06243820 03099190 00734890
232 C -55630480 09121960 -01183850
233 C -67093700 -00820670 -00216620
234 H -29190680 19788790 -00523060
235 H -47585750 -18457830 -00280540
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
236 H -19957420 -21330620 01080960
237 H -01855890 -01749040 09467110
238 H -01552550 -00588810 -08403410
239 H -04873010 13871690 01495830
240 H -56089130 16206320 07133010
241 H -56138950 14741530 -10537820
242 H -67166660 -07721620 -08684940
243 H -66822690 -06321250 09229630
244 H -76386690 04939410 -00509970
The total electronic energy is calculated to be -819347693637 au
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Table S3 Binding constants Ka and Gibbs free energies G of POP5A with
UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K
ligand L-I L-II L-III
Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b
G c (kJmol) -195 -200 -216
a The binding constants were obtained by UV-vis titration experiments
b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3
c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values
using the equation ΔG = -RT ln Ka
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
[POP5A]total
(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4
L-I
UIL (E) 0535 529 123 250 493
iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5
iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4
L-II
UIL (E) 321 267 452 673 847
iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5
iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4
L-
III
UIL (E) 877 340 546 739 893
iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5
iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5
Table S4 Calculated values of (iquest)
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
The complex structure L-I sup UO22+ was optimized by the density functional theory
(DFT) method by employing the Gaussian 09 program [1]
Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+
Center number
SymbolCoordinates (Angstroms)
X Y Z
1 C -07160000 -28706000 32338000
2 C 04927000 -32089000 25844000
3 C 04638000 -38948000 13664000
4 C -07368000 -42523000 07535000
5 C -19497000 -39098000 13976000
6 C -19166000 -32329000 26249000
7 C -07283000 -20960000 45404000
8 C -07249000 -49634000 -05880000
9 O -31032000 -42823000 07764000
10 O 16583000 -28464000 32154000
11 C -43359000 -40442000 14796000
12 C -55070000 -45876000 06751000
13 P -70572000 -43162000 16496000
14 C 28831000 -32048000 25796000
15 C 40442000 -27535000 34599000
16 P 56602000 -31410000 26695000
17 C -84237000 -44838000 04629000
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
18 C 69536000 -25022000 37744000
19 C -07121000 -39613000 -17294000
20 C 04966000 -34493000 -22526000
21 C 04681000 -25031000 -32816000
22 C -07326000 -20298000 -38103000
23 C -19454000 -25356000 -32848000
24 C -19126000 -34931000 -22614000
25 C -07208000 -09725000 -49000000
26 O -30991000 -20594000 -38303000
27 O 16621000 -39367000 -17119000
28 C -43313000 -26569000 -33881000
29 C -55029000 -20584000 -41517000
30 P -70523000 -29071000 -35986000
31 C 28868000 -34479000 -22536000
32 C 40472000 -41461000 -15518000
33 P 56632000 -35083000 -21575000
34 C -84198000 -18286000 -41185000
35 C 69563000 -43561000 -12036000
36 C -07126000 21851000 37282000
37 C 04948000 14614000 38514000
38 C 04641000 00916000 41301000
39 C -07376000 -06001000 42796000
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
40 C -19493000 01200000 41507000
41 C -19143000 14959000 38844000
42 C -07220000 36670000 33948000
43 O -31039000 -05843000 43118000
44 O 16613000 21714000 36981000
45 C -43355000 01598000 43010000
46 C -55082000 -07721000 45663000
47 P -70568000 02408000 46114000
48 C 28852000 14583000 38589000
49 C 40467000 24334000 36960000
50 P 56618000 15593000 38116000
51 C -84244000 -09370000 43973000
52 C 69564000 28053000 35416000
53 C -07087000 04224000 -42989000
54 C 04996000 10791000 -39742000
55 C 04705000 23506000 -33936000
56 C -07303000 29996000 -31078000
57 C -19429000 23432000 -34269000
58 C -19096000 10733000 -40198000
59 C -07189000 43631000 -24396000
60 O -30970000 30096000 -31450000
61 O 16654000 04150000 -42714000
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
62 C -43284000 24032000 -35770000
63 C -55008000 33141000 -32462000
64 P -70507000 25203000 -38738000
65 C 28898000 10821000 -39746000
66 C 40504000 01975000 -44189000
67 P 56671000 09699000 -40009000
68 C -84172000 33535000 -30127000
69 C 69594000 -02010000 -45113000
70 C -07081000 42225000 -09272000
71 C 04999000 41136000 -02017000
72 C 04698000 39524000 11868000
73 C -07316000 38823000 18917000
74 C -19436000 39857000 11682000
75 C -19093000 41596000 -02225000
76 O -30978000 39231000 18886000
77 O 16661000 41890000 -09246000
78 C -43293000 41469000 11786000
79 C -55016000 41117000 21474000
80 P -70506000 44700000 11998000
81 C 28905000 41095000 -01986000
82 C 40517000 42575000 -11767000
83 P 56676000 41057000 -03099000
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
84 C -84182000 39079000 22568000
85 C 69608000 42324000 -15800000
86 H 13786000 -41540000 08514000
87 H -28335000 -29535000 31258000
88 H 01525000 -23546000 51329000
89 H -16141000 -23742000 51152000
90 H 01567000 -56060000 -06487000
91 H -16099000 -55970000 -06756000
92 H -42735000 -45321000 24609000
93 H -44683000 -29707000 16439000
94 H -53756000 -56536000 04585000
95 H -56270000 -40556000 -02755000
96 H 29104000 -42931000 24329000
97 H 29503000 -27232000 15968000
98 H 39874000 -32209000 44493000
99 H 40254000 -16664000 35858000
100 H -84719000 -55047000 00711000
101 H -82600000 -37968000 -03720000
102 H -93642000 -42517000 09703000
103 H 79300000 -28219000 33995000
104 H 68996000 -14120000 37491000
105 H 68238000 -28720000 47958000
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
106 H 13828000 -20928000 -36867000
107 H -28294000 -38815000 -18393000
108 H -16057000 -10848000 -55300000
109 H 01608000 -11120000 -55301000
110 H -42678000 -37405000 -35522000
111 H -44637000 -24850000 -23157000
112 H -53700000 -21768000 -52328000
113 H -56251000 -09911000 -39350000
114 H 29117000 -36489000 -33333000
115 H 29572000 -23642000 -21034000
116 H 39933000 -52311000 -16942000
117 H 40241000 -39339000 -04781000
118 H -93597000 -22417000 -37420000
119 H -82562000 -08239000 -37186000
120 H -84691000 -17666000 -52102000
121 H 79332000 -40948000 -16201000
122 H 68968000 -39937000 -01754000
123 H 68308000 -54423000 -12387000
124 H 13779000 -04796000 42185000
125 H -28304000 20595000 37716000
126 H -16067000 41295000 38375000
127 H 01599000 41487000 38237000
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
128 H -44654000 06486000 33308000
129 H -42735000 09418000 50690000
130 H -56288000 -15100000 37651000
131 H -53781000 -13097000 55121000
132 H 29067000 09949000 48545000
133 H 29579000 06636000 31072000
134 H 39944000 32322000 44441000
135 H 40233000 28867000 26998000
136 H -84760000 -16282000 52446000
137 H -82589000 -15158000 34843000
138 H -93640000 -03813000 43327000
139 H 79326000 23475000 37248000
140 H 68986000 31199000 24977000
141 H 68312000 36614000 42111000
142 H 13851000 28635000 -31298000
143 H -28263000 05521000 -42596000
144 H 01634000 49186000 -27663000
145 H -16032000 49281000 -27419000
146 H -44609000 14373000 -30804000
147 H -42634000 22225000 -46579000
148 H -56210000 34417000 -21644000
149 H -53706000 43041000 -36972000
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
150 H 29150000 20456000 -45016000
151 H 29598000 12765000 -28979000
152 H 39968000 -00054000 -54943000
153 H 40265000 -07565000 -38826000
154 H -93575000 28667000 -32865000
155 H -82535000 32889000 -19333000
156 H -84665000 44096000 -32963000
157 H 79365000 02752000 -43911000
158 H 68991000 -10672000 -38494000
159 H 68341000 -05025000 -55554000
160 H 13840000 38571000 17563000
161 H -28256000 42286000 -07926000
162 H -42651000 51200000 06745000
163 H -44613000 33774000 04120000
164 H -53699000 48441000 29516000
165 H -56229000 31213000 26006000
166 H 29171000 49073000 05560000
167 H 29587000 31446000 03176000
168 H 39959000 52154000 -17057000
169 H 40312000 34496000 -19150000
170 H -93584000 40210000 17097000
171 H -82560000 28603000 25258000
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
172 H -84663000 45012000 31754000
173 H 79376000 42660000 -10894000
174 H 69022000 33359000 -22003000
175 H 68346000 51327000 -21886000
176 O -69996000 13627000 35958000
177 O -70023000 -30008000 23980000
178 O -69984000 -32214000 -21181000
179 O -69951000 10164000 -37040000
180 O -69966000 38485000 -01800000
181 C -71975000 -57637000 27656000
182 C -71967000 08490000 63348000
183 C -71865000 62974000 11511000
184 C -71920000 30317000 -56283000
185 C -71895000 -44091000 -46403000
186 H -81258000 -56806000 33378000
187 H -72098000 -67043000 22071000
188 H -63630000 -57770000 34720000
189 H -81240000 14201000 64345000
190 H -72100000 00253000 70545000
191 H -63610000 15146000 65674000
192 H -81145000 65697000 06405000
193 H -71968000 67287000 21563000
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
194 H -63512000 67214000 05872000
195 H -81217000 26290000 -60400000
196 H -72019000 41206000 -57328000
197 H -63591000 26234000 -62070000
198 H -81179000 -49300000 -43899000
199 H -71996000 -41612000 -57057000
200 H -63547000 -50854000 -44372000
201 O 57224000 03778000 28484000
202 O 57293000 -25942000 12473000
203 O 57257000 -19859000 -20749000
204 O 57330000 28277000 05208000
205 O 57300000 13641000 -25282000
206 C 58451000 10441000 55570000
207 C 58361000 -49610000 27239000
208 C 58474000 -41203000 -38713000
209 C 58544000 24095000 -51137000
210 C 58479000 56103000 07143000
211 H 50885000 56370000 14995000
212 H 68342000 56054000 11863000
213 H 57582000 65130000 01030000
214 H 50954000 31660000 -48998000
215 H 68408000 28552000 -49586000
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
216 H 57691000 21083000 -61619000
217 H 50875000 -36820000 -45228000
218 H 68335000 -38362000 -42492000
219 H 57607000 -52102000 -39087000
220 H 50757000 -54422000 21042000
221 H 68217000 -52368000 23387000
222 H 57458000 -53332000 37486000
223 H 50855000 03055000 58242000
224 H 68313000 05922000 56950000
225 H 57577000 19023000 62297000
226 U 57561000 00034000 -00041000
227 O 40296000 00045000 -00078000
228 O 74727000 00016000 -00029000
The total electronic energy is calculated to be -3365085541640 au
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions
Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each
metal ions and 12 times 10-3 M in total concentration in 10 M HNO3
Metal ions C8mimNTf2
SFL-I SFL-II SFL-III
Sm 19times102 22times103 26times103
Ce 14times102 16times103 18times103
La 61 70times102 37times102
Pr 16times102 18times103 21times103
Er 11times102 16times103 18times103
Nd 91 10times103 12times103
Yb 23 82times102 17times102
Eu 47 54times102 62times102
Gd 31 14times103 16times103
Lu 56 15times103 32times102
Th 9 33times102 12times102
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)
separation
Organic phase Aqueous phase SFa Refs
29times10-4 M calix[4]arenes-based
ligand (B4boctL4) in chloroform
1times10-4 M metal ions in 1 M
HNO335 M NaNO3
11a [4]
5times10-5 M tripodal-based
phosphine oxide in 12-
dichloroethane
1times10-5 M metal ions in 4 M
NH4NO3
89 a [5]
1times10-3 M phenylphosphinate in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
17b [6]
5times10-4 M diphosphine dioxide in
12-dichloroethane
2times10-5 M metal ions in 3 M
HNO3
390b [7]
106times10-4 M calix[6]arenes-based
ligand (B6bL6) in chloroform
11times10-4 M metal ions in 3
M HNO305 M NaNO3
059 a [8]
1times10-3 M pillararenes-based
ligand (POP5A 1b) in
dichloromethane
1times10-4 M metal ions in 1 M
HNO3
135 a [9]
5times10-4 M pillararenes-based
ligand (POP5A 1b) in
C8mimNTf2
1times10-4 M metal ions in 1 M
HNO3
330 a This
work
a SF Separation factor values of UO22+ with respect to Th4+
b SF Separation factor values of Th4+ with respect to UO22+
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
References
[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE
Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci
GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J
Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J
Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA
Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers
KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP
Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M
Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts
RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski
RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ
Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J
Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010
[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New
relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-
299
[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based
pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367
[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S
Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl
pendant arms and its complexation properties towards f-elements Polyhedron 56
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383
(2013) 123-133
[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets
Extraction properties of b-aminophosphine oxides towards lanthanides and
alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941
[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of
extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with
bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53
(2011) 264-268
[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of
U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-
phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-
364
[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties
and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene
bearing phosphinoyl pendants Extraction capability of the calixarene toward f
elements J Phys Chem B 112 (2008) 10976-10988
[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L
Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent
extraction separation of f-block elements from acidic media RSC Adv 3 (2013)
12376-12383