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Materials Design Combinatory Approach Towards Organic Polymer Luminescent · 2019-07-18 ·...
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Electronic Supplementary Information for
Combinatory Approach Towards Organic Polymer Luminescent Materials DesignTao Wang,a,b Xiaoge Su,c,d Xuepeng Zhang,a Wenhuan Huang,a Linkun Huang,a Xingyuan Zhang,*b Xiang Sun,*c,d Yi Luoa and Guoqing Zhang*aHefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China. E-mail: [email protected] (G. Zhang)bDepartment of Polymer Science and Engineering, University of Science and Technology of China, Hefei, China. E-mail: [email protected] (X. Zhang)cDivision of Arts and Science, NYU Shanghai, Shanghai, China. Email: [email protected] (X. Sun) dNYU-ECNU Center for Computational Chemistry, NYU Shanghai, Shanghai, China.
Supplementary Figures and Tables
40 60 80Temperature (C)
CZBP-PLA CZNI-PLA CZAQ-PLA
52.0 C
51.8 C
51.5 C
Figure S1. DSC curves of CZBP-PLA, CZNI-PLA, CZAQ-PLA measured at 10 °C/min under N2 atmosphere.
450 500 550 600 650 700 750 8000.0
2.0x105
4.0x105
6.0x105
8.0x105
1.0x106
Emis
sion
Inte
nsity
(CPS
)
Wavelenghth (nm)
THF EtOAc DCM DMF
400 450 500 550 600 650 7000.0
5.0x105
1.0x106
1.5x106
2.0x106
2.5x106
Emis
sion
Inte
nsity
(CPS
)
Wavelength (nm)
THF EtOAc DCM DMF
(a) (b)
Figure S2. Steady-state emission spectra of CZNI-PLA (a, Ex slit 6 nm, Em slit 6 nm) and CZBP-PLA (b, Ex slit 3 nm, Em slit 4 nm) in THF, EtOAc, DCM and DMF, respectively.
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2019
300 400 500 6000.0
0.2
0.4
0.6
0.8
1.0
Nor
mal
ized
Inte
nsity
Wavelength (nm)
DCM THF EtOAc DMF
Figure S3. Normalized UV-vis absorption of CZAQ-PLA in dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EtOAc), and N, N’-dimethyl formamide (DMF).
400 450 500 550 600 6500.0
2.0x104
4.0x104
6.0x104
8.0x104
Inte
nsity
Wavelength (nm)
1 ms 3 ms 5 ms 7 ms
450 500 550 600 650 7000.0
5.0x103
1.0x104
1.5x104
2.0x104
2.5x104
Inte
nsity
Wavelength (nm)
10 ms 20 ms 30 ms 40 ms
CZNI-PLA
577 nm
CZBP-PLA
445 nm
450 500 550 600 650 7000
1x104
2x104
3x104
4x104
Inte
nsity
Wavelength (nm)
50 μs 60 μs 70 μs 80 μs
CZAQ-PLA586 nm
575 nm
(a) (b) (c)
Figure S4. Delayed emissions of CZNI-PLA (a), CZBP-PLA (b), and CZAQ-PLA (c) at 298 K in vacuum with various delayed time.
0.0 0.1 0.2 0.3 0.4100
101
102
103
104
Cou
nts
Time (s)
Fit Decay
τ422nm=29.8 ms
Figure S5. Time-resolved PL decay curves of CZBP-PLA measured at 422 nm in vacuum at 77 K.
T1
H−3 H
L
T2
H−8 H−4
Figure S6. Calculated frontier molecular orbitals of CZAQ-OH for electronic transition of T1 and T2 based on optimized T1 structure at ωB97XD/6-311G* level.
0 50 100 150 200 250 300
0
20
40
60
80
100
Num
ber (
%)
Diameter (nm)
CZBP-PLA CZNI-PLA CZAQ-PLA
Figure S7. Particle diameters of CZBP-PLA, CZNI-PLA, and CZAQ-PLA nanoparticles, respectively.
Table S1. Lifetime data for CZBP-PLA, CZNI-PLA, CZAQ-PLA films.
λaair
(nm)λb
vacuum (nm)
λc77k
(nm)λe
delay (nm)
τeair
(S)τf
vacuum(S)
τg77k
(S)τh
delay(S)
CZBP-PLA
445 445 445 484
7.27608410-
5
(58.47%)4.2635310-7
(0.98%)2.54677310-
4
(40.54%)
8.4056310-3
(40.95%)0.0280176(35.08%)
1.84248210- -3
(15.87%)
1.63887410-
2
(4.97%)5.01750910-
-2 (58.58%)
0.1238015(36.45%)
1.76727310-
2
(5.05%)0.0545019(55.58%)
0.1446192(39.37)
CZNI-PLA
512 526 518 576
8.42001710-
9
(18.23%)6.48413310-
10
(1.68%)1.86819410-
1.26974810-
2
(9.72%)7.68365310-
2
(90.10%)9.41750410-
1.92174610-
8
(85.89%)2.98346610-
8
(14.11%)
0.1151937(7.40%)
0.2265507(92.60%)
8
(80.09%)5
(0.18%)CZAQ-PLA
576 577 580 582
1.13197810-
5
(28.12%)4.61118110-
5
(70.99%)6.48826310-
8
(0.89%)
1.2867210-5
(31.37%)6.49666810-
8
(0.58%)4.89376810-
5
(68.05%)
1.57555910-
2
(9.47%)0.1179909(90.26%)1.06806810-
4
(0.27%)
1.76805210-
2
(9.13%)0.1218552(90.63%)7.80366210-
5
(0.24%)
a. steady-state emission maxima under air at 298 K (λex = 365 nm);
b. steady-state emission maxima under vacuum at 298 K (λex = 365 nm);
c. steady-state emission maxima under vacuum at 77 K (λex = 365 nm);
d. delayed emission maxima under vacuum at 77 K (λex = 365 nm);
e. measured lifetimes of steady-state emission in air at 298 K;
f. measured lifetimes of steady-state emission in vacuum at 298 K;
g. measured lifetimes of steady-state emission in vacuum at 77 K;
h. measured lifetimes of delayed emission in vacuum at 77 K.
Table S2. Nanoparticle sizes of PLAs.
PLA Diameter (nm)CZBP-PLA 30CZNI-PLA 66CZAQ-PLA 39
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
0
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3.01
2.02
2.00
2.00
2.00
1.00
2.00
NO O
Cl
a
b
c
d
e
fg
h
i
a
bcd
e,g
i f,h
DMSOH2O
Figure S8. 1H NMR spectrum of ClNNI in d6-DMSO.
6.26.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.6f1 (ppm)
-200
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1.00
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-200
0
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2.00
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3.00
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4.00
2.00
1.00
N
O
OH
O
a
bc
d
ef
gh
i
jk
lm
n
op
qr
s
a
DMSOH2O
cb
n,l
fid,h,ejr,p
g
k,m,s,o
q
Figure S9. 1H NMR spectrum of CZBP-OH in d6-DMSO.
2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-500
0
500
1000
1500
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4000
4500
5000
5500c z - a q - 1 0 . 1 . f i d
2.00
2.00
1.00
1.00
1.04
3.01
1.00
2.00
3.01
3.00
N
O
OH
O
O
ab
c
d
ef
gh
i
jk
l
m
n
op
q
a bc
DMSO
H2O
fi
a,h,e
jo,pm,n,qk,l,g
Figure S10. 1H NMR spectrum of CZAQ-OH in d6-DMSO.
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-200
0
200
400
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800
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1400
1600
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2400
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2800
3000
3200
3.00
2.01
2.00
4.02
2.01
1.02
1.01
2.00
3.00
1.01
1.01
1.00
1.00
1.00
1.00
NO O
N
O
OHa
bc
de
f
gh
ij
k
l
mno
pq
rs
s
rqpbc
a
fide,h,j
knsl g o
DMSO
H2O
Solvent2-ethoxyethanol
Solvent2-ethoxyethanol
Figure S11. 1H NMR spectrum of CZNI-OH in d6-DMSO.
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-2000
0
2000
4000
6000
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10000
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16000
18000
20000
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30000
32000
34000
36000
1125
.11
4.03
375.
28
1.01
1.02
3.03
1.02
1.99
1.03
2.00
1.96
2.00
1.00
6.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.6f1 (ppm)
-100
0
100
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1600
1.01
1.02
3.03
1.02
1.99
1.03
2.00
1.96
2.00
1.00
Figure S12. 1H NMR spectrum of CZBP-PLA in CDCl3.
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
-1000
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
11000
12000
13000
CDCl3
Figure S13. 13C NMR spectrum of CZBP-PLA in CDCl3.
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f2 (ppm)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
f1 (
ppm
)
Figure S14. Section of 1H-1H COSY NMR spectrum of CZBP-PLA in CDCl3.
-1.5-0.50.51.52.53.54.55.56.57.58.59.510.5f2 (ppm)
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
f1 (
ppm
)
Figure S15. Section of 1H-13C COSY NMR spectrum of CZBP-PLA in CDCl3.
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
-1000
0
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13000
14000
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870.
11
1.94
1.91
290.
22
1.04
1.03
3.02
1.00
2.02
1.00
3.04
2.02
6.06.16.26.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.1f1 (ppm)
-50
0
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700
750
1.04
1.03
3.02
1.00
2.02
1.00
3.04
2.02
Figure S16. 1H NMR spectrum of CZAQ-PLA in CDCl3.
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
-500
0
500
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1500
2000
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3000
3500
4000
4500
5000
5500
6000
6500
7000CDCl3
Figure S17. 13C NMR spectrum of CZAQ-PLA in CDCl3.
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f2 (ppm)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
f1 (
ppm
)
Figure S18. Section of 1H-1H COSY NMR spectrum of CZAQ-PLA in CDCl3.
-1.5-0.50.51.52.53.54.55.56.57.58.59.510.5f2 (ppm)
0
10
20
30
40
50
60
70
80
90
100
110
120
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150
f1 (
ppm
)
Figure S19. Section of 1H-13C COSY NMR spectrum of CZAQ-PLA in CDCl3.
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1000
0
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702.
17
4.00
1.96
233.
76
1.05
1.03
1.01
3.01
1.03
1.01
1.06
1.00
1.00
1.00
6.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.2f1 (ppm)
0
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350
400
450
1.05
1.03
1.01
3.01
1.03
1.01
1.06
1.00
1.00
1.00
Figure S20. 1H NMR spectrum of CZNI-PLA in CDCl3.
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
-500
0
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4500
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5500
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6500
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8500CDCl3
Figure S21. 13C NMR spectrum of CZNI-PLA in CDCl3.
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f2 (ppm)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
f1 (
ppm
)
Figure S22. Section of 1H-1H COSY NMR spectrum of CZAQ-PLA in CDCl3.
-1.5-0.50.51.52.53.54.55.56.57.58.59.510.5f2 (ppm)
0
10
20
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40
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60
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80
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100
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120
130
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150
f1 (
ppm
)
Figure S23. Section of 1H-13C COSY NMR spectrum of CZAQ-PLA in CDCl3.
Figure S24. ESI mass spectrum of CZBP-OH.
Figure S25. ESI mass spectrum of CZAQ-OH.
Figure S26. ESI mass spectrum of CZNI-OH.
6.5 7.0 7.5 8.0 8.5 9.0 9.5
RI
Elution time (min)6.5 7.0 7.5 8.0 8.5 9.0 9.5
RI
Elution time (min)
B
6.5 7.0 7.5 8.0 8.5 9.0 9.5
RI
Elution time (min)
B
(a) (b) (c)
Figure S27. GPC traces for CZBP-PLA (a), CZNI-PLA (b), CZAQ-PLA (c).