Self-assembly formation of mechanically interlocked [2 ... · PDF fileSelf-assembly formation...
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Self-assembly formation of mechanically interlocked [2]- and [3]catenanes using lanthanide ion [Eu(III)] templation and ring closing metathesis reactions
Christophe Lincheneau, Bernard Jean-Denis and Thorfinnur Gunnlaugsson*
Electronic Supplementary Information
ESI.1: Molecular models of the complex L13.Eu and the catenane resulting from a triple RCM, obtained from calculation in the MM2 force field with Chem3D.
ESI.2: MM2 molecular models of the different isomers resulting from a triple RCM, depending on the number of inter- and intra-ligands RCM.
+3
Caténation par macrocyclisation intra-ligands
Caténation avec contributions inter-ligands
Démétallation Démétallation
- Ln - Ln
Isolé Non détecté Non détecté Non détecté
Non détecté Forme majoritaire
potentielle des adduits 15
3"inter(ligand"RCM"
+3
Caténation par macrocyclisation intra-ligands
Caténation avec contributions inter-ligands
Démétallation Démétallation
- Ln - Ln
Isolé Non détecté Non détecté Non détecté
Non détecté Forme majoritaire
potentielle des adduits 15
2"inter(ligand"RCM"1"intra(ligand"RCM" 3"intra(ligand"RCM"
+3
Caténation par macrocyclisation intra-ligands
Caténation avec contributions inter-ligands
Démétallation Démétallation
- Ln - Ln
Isolé Non détecté Non détecté Non détecté
Non détecté Forme majoritaire
potentielle des adduits 15
3"intra(ligand"RCM"
+
3
Caténation par
macrocyclisation intra-ligands
Caténation avec contributions
inter-ligands
Dém
étallation
Dém
étallation
- Ln
- Ln
Isolé N
on détecté N
on détecté
Non détecté
Non détecté
Forme m
ajoritaire
potentielle des adduits
15
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ESI.3: Synthesis in 5 steps from the triethylenhglycol of the precursor 2 and synthesis protocols of compound 1-5, L1, L13.Eu and Cat• L23.Eu.
2,6-Pyridinedicarboxylic acid chloride (1):
2,6-Pyridinedicarboxylic acid (5 g, 29.9 mmol) was refluxed overnight in
thionylchloride (50 ml). The mixture was reduced to dryness under reduced
pressure, before compound 1 was obtained as a white powder in 99% yield (5.97
g). Calculated for C7H3NO2Cl2: [M+H]+ m/z = 202.9542; Found: 202.9563; δH (400 MHz, MeOD-
D4, 298.2 K) 8.39 (2H, d, J = 7.56 Hz, Ar-H4), 8.22 (1H, t, J = 7.56 Hz, Ar-H2); Selected IR bands
(cm-1): 1751s (υCO).
2-(2-(2-(allyloxy)ethoxy)ethoxy)ethanol (3):
To a solution of triethylene glycol (30g, 200 mmol) in toluene
(20 mL) at room temperature, allyl chloride (18.04 mL, 219.7
mmol) and NaOH (16 g, 400 mmol) were added. The resulting mixture was refluxed for 3 days.
Upon filtration of a white residue and evaporation of the solvent under reduced pressure, the brown
oil was dissolved in CH2Cl2 and washed with brine (50 mL) and distilled water (50 mL). The
resulting orange oil was further purified by silica column chromatography using hexane-EtOAc
from 7:3 to 1:1 gradient, yielding a colourless oil (10.38 g, 54.6 mmol, 27.3% yield) HRMS (m/z)
(ES+) Calculated for C9H19O4 [M+H+]+ m/z = 191.1286, Found 191.1286; δH (CDCl3; 400 MHz):
OHO
OHO
OHO
OO
OTsO
OO
N3
OO
ONH2
OO
O
3 4
5 2
NaOH, Toluene
Δ, 3 days
TsCl, pyridine
DCM, R.T. 48h
NaN3, CH3CN
Δ, 4 days
PPh3, THF
0°C→R.T., 4 days
NH2
OO
O
NCl
O
Cl
O 1
2
+
L1
i" ii"
L2
N O
HN
O
NH
O
O
O
O
22
N O
HN
O
NH
O
O
O
O
22
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5.95 (m, 1H, CH=CH2), 5.28 (m, 2H, CH=CH2), 4.06 (m, 2H, CH2CH=CH2), 3.62 (m, 12H, CH2);
δc (CDCl3; 100 MHz): 134.6, 117.1, 72.5, 70.2-70.5, 61.6.; IR νmax (cm-1) = 3376, 2870, 1648, 1350,
1245, 1116, 1064, 934, 885.
2-(2-(2-(allyloxy)ethoxy)ethoxy)ethyl-4-methylbenzenesulfonate (4):
3 (500 mg, 2.6 mmol) and 5 equivalents of TsCl (2.5 g, 13 mmol)
were dissolved in dichloromethane (20 mL) before the resulting
mixture was stirred for 15 minutes. To that solution, pyridine (2.13 mL, 26 mmol) was added drop
wise before the resulting mixture was stirred at room temperature for 48h. The pyridine was
quenched with 1M HCl (1 mL) before the solvents were removed under reduced pressure. The
resulting mixture was extracted with CH3Cl (50 mL) before the organic layer was washed with H2O
(2×50 mL) and dried over MgSO4. Compound 4 was isolated as a yellow oil in 45% yield (404 mg,
1.17 mmol), after purification via silica column chromatography using CH2Cl2-CH3OH (9-1) as
eluent. HRMS (m/z) (ES+) Calculated for C16H24O6S [M+Na+]+ m/z = 367.1191, Found 367.1132;
δH (CDCl3; 400 MHz): 7.79 (d, 2H, 3J = 8.0 Hz, Ar-H), 7.33 (d, 2H, 3J = 8.0 Hz, Ar-H), 5.89 (m,
1H, CH=CH2), 5.28 (m, 1H, CH=CH2), 5.18 (m, 1H, CH=CH2), 4.16 (m, 2H, CH2-OTs), 4.01 (m,
2H, CH2CH=CH2), 3.68-3.59 (m, 12H, CH2), 2.44 (s, 3H, Ar-CH3); δc (CDCl3; 100 MHz): 144.3,
134.2, 132.5, 129.38, 127.5, 117.1, 71.8, 70.3, 70.2, 68.9, 68.8, 68.2, 21.2; IR νmax (cm-1) = 3389,
2876, 1598, 1452, 1351, 1211, 1188, 1120, 1095, 1033, 916, 816, 683, 662.
3-(2-(2-(2-azidoethoxy)ethoxy)ethoxy)propen-1-ene (5):
5 was synthesised by refluxing 4 (300 mg, 0.87 mmol), with NaN3
(680 mg, 10 mmol, 12 eq) in CH3CN for 4 days. The resulting white
suspension was isolated by filtration before the solvent was removed under reduced pressure. The
resulting yellow oil was dissolved in CH2Cl2 and washed twice with H2O (2 × 50 mL) to give 5 as a
yellow oil in 74% yield (140 mg, 0.64 mmol). δH (CDCl3; 400 MHz): 5.90 (m, 1H, CH=CH2), 5.28
(m, 1H, CH=CH2), 5.16 (m, 1H, CH=CH2), 4.02 (m, 2H, CH2CH=CH2), 3.68-3.59 (m, 12H, CH2),
3.38 (m, 2H, N3-CH2); δc (CDCl3; 100 MHz): 134.2, 116.7, 71.8, 70.3, 70.2, 69.5, 68.9, 50.2, 42.3;
IR νmax (cm-1) = 3422, 2866, 1452, 1348, 1287, 1248, 1094, 995, 927, 881, 838
3-(2-(2-(2-aminoethoxy)ethoxy)ethoxy)propen-1-ene (2):
To a solution of 5 (1.24 g, 5.5 mmol) in THF (50 mL) at 0ºC, PPh3
(1.66 g, 6.1 mmol) was added portionwise and the resulting mixture was
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stirred at room temperature for 12h. The resulting oil was dissolved in H2O and washed with
toluene (2 × 20mL). 2 was obtained as a yellow oil after evaporation of the aqueous layer under
reduced pressure (759 mg, 4.0 mmol, 73%). δH (CDCl3; 400 MHz): 5.89 (m, 1H, CH=CH2), 5.28
(m, 1H, CH=CH2), 5.16 (m, 1H, CH=CH2), 4.01 (m, 2H, CH2CH=CH2), 3.65-3.49 (m, 12H, CH2),
2.85 (m, 2H, H2N-CH2); δc (CDCl3; 100 MHz): 134.3, 116.7, 114.8, 71.8, 70.3, 70.2, 69.6, 69.0,
50.2, 42.3; IR νmax (cm-1)= 3360, 2666, 1665, 1565, 1445, 1348, 1297, 1248, 1091, 995, 924, 881,
818.
N,N’-bis(2-(2-(2-(allyloxy)ethoxy)ethoxy)ethyl)pyridine-2,6-dicarboxamide (L1):
To a solution of 1 (300 mg, 1.5 mmol) and
triethylamine (270 mg, 6 mmol, 4 eq) at 0ºC in CH2Cl2
(50 mL) was added a solution of 2 (612 mg, 3.2 mmol, 2.2 eq) and triethylamine (148 mg, 1.6
mmol, 1.1 eq) in CH2Cl2 (20 mL) dropwise over a period of 15 min. The resulting mixture was
allowed to reach room temperature before being stirred for 48h. The solvent was removed under
reduced pressure before the resulting brown oil was re-dissolved in CH2Cl2 and washed with
distilled H2O (2 × 50 mL). The organic layer was dried over MgSO4 before the solvent was removed
and L1 was then obtained as an yellow oil in 48% yield (360 mg, 0.7 mmol). HRMS (m/z) (ES+)
Calculated for C25H39O8N3 [M+Na+]+ m/z = 532.2635, Found 532.2812; δH (CDCl3; 400 MHz):8.57
(s, 2H, NH), 8.35 (d, 3J = 7.6 Hz, 1H, Pyr-H), 8.03 (t, 3J = 8.2 Hz, 2H, Pyr-H), 5.88 (m, 2H,
CH=CH2), 5.26 (m, 2H, CH=CH2), 5.15 (m, 2H, CH=CH2), 3.98 (m, 2H, CH2CH=CH2), 3.72-3.66
(m, 20H, CH2), 3.59 (m, 2H, HN-CH2); δc (CDCl3; 100 MHz): 169.4, 151.3, 134.6, 126.5, 117.2,
72.0, 70.3, 70.2, 70.0, 69.2, 67.3, 45.4, 39.3; IR νmax (cm-1)= 3550, 3320, 2867, 1665, 1532, 1445,
1349, 1247, 1093, 998, 926, 846, 749, 679.
Complex, L13.Eu:
Ligand L1 (50 mg, 0.098 mmol) and Eu(CF3SO3)3 (19.6 mg; 0.032 mmol) were refluxed in CH3CN
(10 mL) for 12h. The solvent was removed under reduced pressure. The resulting concentrated
solution was poured over diethylether before complex L13.Eu was collected in 32% yield as pale
yellow oil (22.2 mg; 0.012 mmol). δH (CDCl3; 600 MHz): 8.53; 8.37; 8.05; 7.36; 5.88; 5.29; 4.04;
3.74-3.59; 3.52. IR νmax (cm-1): 3510, 3285; 1667; 1547; 1346; 1260; 1093; 1005; 980; 937; 752;
677.
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Catenation of L13.Eu (Cat•L23.Eu):
Anhydrous complex L13.Eu (26 mg, 0.013 mmol) was dissolved in distilled CH2Cl2 (20 mL),
under an inert atmosphere. To this solution the 2nd generation Grubb’s catalyst (3.1 mg, 3.6 ×10-3
mmol, 0.3 eq) was added drop wise over a period of 5 minutes. The resulting mixture was stirred at
room temperature for 3 days under an inert atmosphere. The CH2Cl2 was removed under reduced
pressure and the resulting brown oil was dissolved in H2O. The aqueous layer was washed with
ethyl acetate (20 mL) before the H2O was removed under reduced pressure. The resulting orange oil
was triturated in CH2Cl2 and Cat•L23.Eu was obtained as a crude white solid (7 mg). The
dichloromethane was removed under reduced pressure and the compound Cat•L23 was obtained as
crude yellow oil (10 mg).
Cat•L23.Eu: HRMS: Calculated for C70H106N9F9O28SEu [M3+ + CF3SO3- + OH-]+ 1762.6044,
Found 1761.6688 δH (CDCl3; 600 MHz): 8.93; 8.34; 7.02; 7.36; 5.88; 5.29; 4.06; 3.73-3.69; 3.50.
IR νmax (cm-1): 3510, 3285; 1667; 1547; 1346; 1260; 1093; 1005; 980; 937; 752; 677.
Cat•L23: HRMS: Calculated for C69H105N9O24 [M + Na+]+ 1466.7170, Found 1466.7152 δH
(CDCl3; 600 MHz): 8.30; 8.15; 5.82; 4.00; 5.88; 5.29; 4.06; 3.73-3.71; 3.24. IR νmax (cm-1): 3552,
3314; 2865; 1665; 1532; 1445; 1345; 1310; 1245; 1099; 998; 852, 740.
Macrocyle L2:
Ligand L1 (50.8 mg, 0.1 mmol) was dissolved in freshly
distilled CH2Cl2 (100 mL), under inert atmosphere. To this
solution the 2nd generation Grubb’s catalyst (12.7 mg, 1.4
×10-3 mmol, 0.14 eq) was added drop wise over a period of
5 minutes. The CH2Cl2 is removed under reduced pressure
and the resulting mixture is washed with H2O (2×50 mL).
The organic layer was washed over MgSO4 and L2 was
obtained as brown oil (38.4 mg, 0.08 mmol, 80%). HRMS:
Calculated for C23H35N3O8 [M + Na+]+: 504.2322, Found 504.2316; δH (CDCl3; 400 MHz): 8.57 (s,
2H, NH), 8.34 (d, 3J = 7.7 Hz, 2H, Pyr-H), 8.02 (t, 3J = 7.8 Hz, 1H, Pyr-H), 5.89 (s, 2H, CH=CH),
4.07 (m, 4H, CH2CH=CH), 3.74-3.66 (m, 22H, CH2), 3.59 (m, 2H, HN-CH2); δc (CDCl3; 100 MHz):
163.6, 148.4, 138.2, 128.9, 124.2, 70.2, 70.1, 69.9, 69.7, 68.6, 39.0, 29.2; IR νmax (cm-1) = 3550,
3314, 2864, 1663, 1534, 1446, 1349, 1305, 1245, 1176, 1098, 999, 847, 749, 662.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014
ESI.4: Absorption, excitation (λem = 545 and 615 nm) and Emission (λex = 281 nm) spectra of L1 and the resulting Eu3+ and Tb3+ in acetonitrile at C = 2×10-5 M
ESI.5: Absorption, excitation (λem = 545 and 615 nm) and Emission (λex = 281 nm) spectra of L1 and the resulting Eu3+ and Tb3+ in acetonitrile at C = 2×10-5 M
0
0,1
0,2
0,3
0,4
200 250 300 350 400 0
20
40
60
80
100
120
300 400 500 600 700
Wavelength*(nm)*
Em
issi
on
Wavelength*(nm)*
Abs
orpt
ion
a.* b.*
400# 450# 500# 550# 600# 650# 700#0
50
100
150
200
250
300
350
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
0,5
200 300 400 500 600 700
Em
issi
on (a
.u.)
Abs
orba
nce
(a.u
.)
Wavelength (nm)
L1
L13.Ln (UV)
L13.Eu (Emission)
Excitation of L13.Ln
L13.Tb (Emission)
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ESI.6: Evolution of the absorption and delayed emission spectra of a solution of L1 (2×10-5 M in acteonitrile) upon the addition of Eu(CF3SO3)3
ESI.6: Job’s plots experiments, performed by varying the molar fraction of Eu(CF3SO3)3 in solution (Ctot = 2×10-5 M in acetonitrile)
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014
ESI.7: Evolution of the absorption and delayed emission spectra of a solution of L1 (2×10-5 M in acteonitrile) upon the addition of Tb(CF3SO3)3
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014
ESI.8: Job’s plots experiments, performed by varying the molar fraction of Tb(CF3SO3)3 in solution (Ctot = 2×10-5 M in acetonitrile)
ESI.9: Speciation diagram and fit resulting from the data obtained from the UV-vis titration of L1 vs Eu(CF3SO3)3
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014
ESI.10: Speciation diagram and fit resulting from the data obtained from the UV-vis titration of L1 vs Tb(CF3SO3)3
ESI.11: 1H-NMR (CDCl3, 400 MHz) of L1 and L2 and Mass-spectrum obtained in ESMS for L2
N
HN
O
HN
OOO
O O
O O
a
b
c
d
ef
g
a
b,c d
f
g e
N
HN
O
OO
OHN
OO
OO a
b
c
d
ef
gHcis
Htrans
e
f
g a
d b
c
H
(ppm)%
504.2316%
505.2350%
506.2350%
m/z%
3%4%5%6%7%8%9%
500% 505% 510%
100%
50%
0%
%%
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014
ESI.12: 1H-NMR (MeOD-D4, 400 MHz) of Cat•L23
ESI.13: MALDI-ToF (DCTB matrix) Mass-Spectrum of the Cat•L23 compound resulting from an inter-ligand RCM (inset: calculated spectra for Cat•L23 + Na+ and Cat•L23 + K+)
(ppm) 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5
+Na+
+K+
0"
50"
100"
1466,717"
1467,7204"
1468,7237"
1469,7271"
1470,728"
%"
1466 1468 1470 m/z"
1466.7170"
1467.7204"
1468.7237"
1469.7246"0
50
100
1482.6910"
1483.6943"
1484.6977"
1485.7010"
1486.6958"1482 1484 1486
1482.6910"
1483.6943""
1484.6977""
1485.6924"
m/z"
%"
100"
50"
1466.7350"
1467.7489"
1482.7023"
1483.7076"
1484.7133"
1485.7191"
1632.6884"1633.6542"
1634.7094"
Matrix
1400" 1450" 1500" 1550" 1600" 1650" 1700" 1750"1350"0"
m/z"
%"
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014
ESI.14: MALDI-ToF (DCTB matrix) Mass-Spectrum of the Cat•L23.Eu compound resulting from an intra-ligand RCM.
ESI.15: MS.MS spectra obtained for the fragment found at m/z = 1280.4 (Top) and 1761.6 (Bottom) for the [2]-Cat•L22.Eu and [3]-Cat•L23.Eu respectively during the MALDI.ToF analyses
+"CF3SO3("
+"OH("
="
+"CF3SO3("
+"OH("
="
DCTB"matrix"
0"
50"
100"
1760,6019"
1761,6052"
1762,6032"
1763,6066"
1764,6099"
1765,6133"1760" 1762" 1764" 1766"
1762.6044"
1763.6068"
1764.6085"
1760.6019"
0"
50"
100"
1" 2" 3" 4" 5" 6"1279" 1281" 1283" 1285"
"1281.3608"
"1282.3642"
1283.3675"
1279.3594""
1400" 1450" 1500" 1550" 1600" 1650" 1700" 1750"1350"1250" 1300"1200" 1800" 1850" 1900"
m/z"
100"
50"
0"
%"
1278.4253""
1280.4255""
1281.4308""
1570.6774""1571.6812""
1572.6879""1568.4463"" 1761.6686""
1759.6642"1763.6807"
+"2"CF3SO3("
+"H2O"
1910.5735""1430.3364"
+"2"CF3SO3("
+"H2O"
01-Jul-2009Christophe L (TG), CL54A02 in DCTB MSMS m/z 1280
m/z300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350
%
0
100Q-TOF20090701JD017 153 (2.834) Cm (79:185) TOF MSMS 1280.00LD+
104332.2307
1280.5558
1278.5570
449.0727
403.0365
373.0469
474.0926607.1541
509.0796 604.27671236.5271824.2788710.2427632.2104
780.26661029.5519
982.4122884.3478
1281.5559
1284.7693
1289.8344
1291.9476
01-Jul-2009Christophe L (TG), CL54A02 in DCTB MSMS m/z 1 (triflate as ci)
m/z300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
%
0
100Q-TOF20090701JD016 171 (3.167) Cm (13:202) TOF MSMS 1762.00LD+
1181761.8353
1760.8015
332.2307
333.23651717.9016449.0572 631.2217
1762.8385
1762.9156
1763.8419
1763.9344
1771.0291
800# 1300#900# 1400#1000# 1200#1100#600# 700#500#400#300# 1500#
m/z#
1600# 1700# 1800#
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ESI.16: Evolution of the absorption and emission spectra of L13.Eu and Cat•L23.Eu and L13.Eu upon the addition of DTPA (2×10-5 M in acetonitrile)
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014
ESI.17: Mass-spectrum obtained after stirring a solution of L13.Eu with 1 equivalent of DTPA for 30 minutes
ESI.18: Mass-spectrum obtained after stirring a solution of Cat�L23.Eu with 1 equivalent of DTPA for 30 minutes
1280.5294)
1281.5295)
1380.4282)
1278.5175)
1570.8113)
1571.8022)
1572.8372)1566.5741)
1761.8043)
1762.8075)
1282.5686)
978.6592)
1077.5306)
1087.4609)
1105.5387)
100)
50)
0)
%)
1400) 1900)1500) 2000)1600) 1800)1700)1200) 1300)1100)1000)900) 2100)m/z)
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ESI.19: Mass-spectrum (MALDI-ToF) obtained after stirring a solution of L2 with 0.3 equivalent of Eu(CF3SO3)3 for 30 minutes
ESI.20: Mass-spectrum (MALDI-ToF) obtained after stirring a solution of L2 + 0.3 Eu with 1 equivalent of DTPA for 30 minutes
L22.Eu&+&2&CF3SO3&
1411.3087(
1413.3104(
1414.3141(
1415.3130(
1416.3141(
L2.Eu&+&2&CF3SO3&
Matrix&
100(
50(
0(
%(
m/z(
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