Supporting Information
for
The Mixed-Valence Class I Transition and Electrochemistry of
Bis(triphenylamine)-based Aramids Containing Isolated Ether-linkage
by
Hung-Ju Yen, Shiue-Ming Guo and Guey-Sheng Liou*
Functional Polymeric Materials Laboratory, Institute of Polymer Science and Engineering,
National Taiwan University, Taipei, Taiwan
Jen-Chieh Chung, Yu-Chang Liu, Yung-Fang Lu, Yu-Zhen Zeng
Institute of Nuclear Energy Research, Atomic Energy Council, Taoyuan County, Taiwan
Tel: +886-2-336-5315; Fax: +886-2-336-5237; E-mail: gsliou@ntu.edu.tw
List of Contents for Supplementary Material:
Table S1. Inherent Viscosity and Molecular Weights of Polyamides ............................... SI-2
Table S2. Solubility Behavior of Polyamides ................................................................... SI-3
Table S3. Thermal Properties of Polyamides.................................................................... SI-4
Table S4. Optical and Electrochemical Data Collected for Coloration Efficiency
Measurements of Polyamide Ib ..................................................................... SI-5
Figure S1. IR spectra of (a) compound 1, (b) compound 2 and (c) monomer 3. .................... SI-6
Figure S2. 1H NMR and 13C NMR spectra of compound 1 in DMSO-d6.. ...................... SI-7
Figure S3. 1H NMR and 13C NMR spectra of compound 2 in DMSO-d6. .................................. SI-8
Figure S4. H-H COSY and C-H HMQC spectra of compound 2 in DMSO-d6. ..................... SI-9
Figure S5. 1H NMR and 13C NMR spectra of monomer 3 in DMSO-d6...................................... SI-10
Figure S6. H-H COSY and C-H HMQC spectra of monomer 3 in DMSO-d6.. ............... SI-11
Figure S7. IR spectrum (film) of polyamide Ib. ............................................................................................ SI-12
Figure S8. 1H NMR of polyamide Ib in DMSO-d6. .................................................................................... SI-13
Figure S9. Typical TGA curves of polyamide Ib. ......................................................................................... SI-14
Figure S10. DSC curves of polyamide Ia, Ib and Ic.................................................................................. SI-15
Figure S11. Electrochromic behavior by increasing the applied voltage to 1.10 (V vs.
Ag/AgCl) of polyamide Ib thin film (~70 nm in thickness) on the ITO-coated
glass substrate in 0.1 M TBAP/CH3CN ......................................................... SI-16
Figure S12. Calculation of optical switching time at 781 nm at the applied potential, and
current-time curves of polyamide Ib thin film (~80 nm in thickness) on the
ITO-coated glass substrate (coated area: 1.6 cm x 0.6 cm) in 0.1 M
TBAP/CH3CN. ............................................................................................. SI-17
SI-1
Table S1. Inherent Viscosity and Molecular Weights of Polyamides
Code
ηinha (dL/g)
Mwb
Mnb
PDIc
DPd
0.63
191700
109000
1.76
149.1
Ia
0.51
244300
134800
1.81
165.0
Ib
0.43
269100
151200
1.78
159.0
Ic
a
Measured at a polymer concentration of 0.5 g/dL in DMAc at 30 oC.
b
Calibrated with polystyrene standards, using DMF as the eluent at a constant flow rate of 1
ml/min at 70 oC.
c
Polydispersity Index (Mw/Mn).
d
Degree of Polymerization.
SI-2
Table S2. Solubility Behavior of Polyamides
Solubility in various solventa
Code
NMP
DMAc
DMF
m-cresol
THF
CHCl3
Ia






Ib






Ic






I’b






a
Qualitative solubility was tested with 10 mg of a sample in 1 mL of solvent. : soluble at
room temperature, : soluble on heating,partially soluble.  : insoluble even on heating.
SI-3
Table S3. Thermal Properties of Polyamides
Polymera
Tg (oC)b
Td5 (oC)c
Td10 (oC)c
Rw800 (%)d
N2
Air
N2
Air
258
445
435
465
475
53
Ia
252
465
460
500
505
64
Ib
265
480
475
520
525
65
Ic
a
o
The polymer film samples were heated at 300 C for 1 h prior to all the thermal analyses.
b
Midpoint temperature of baseline shift on the second DSC heating trace (rate: 20 oC /min) of
the sample after quenching from 380 oC to 50 oC (rate: 100 oC /min) in nitrogen.
c
Temperature at which 5 % and 10 % weight loss occurred, respectively, recorded by TGA at
a heating rate of 20 oC/min and a gas flow rate of 20 cm3/min.
d
Residual weight percentages at 800 oC under nitrogen flow.
SI-4
Table S4. Optical and Electrochemical Data Collected for Coloration Efficiency
Measurements of Polyamide Ib
cycling timesa
δOD781b
Q (mC/cm2)c
η (cm2/C)d
1
0.763
4.61
166
10
0.763
4.60
166
20
0.753
4.60
164
30
0.746
4.58
163
40
0.740
4.57
162
50
0.734
4.57
161
60
0.732
4.56
161
70
0.731
4.55
161
80
0.728
4.55
160
90
0.725
4.54
160
100
0.716
4.53
158
a
Switching between 0 and 0.99 V (vs Ag/AgCl).
b
Optical density change at 781 nm.
c
Ejected charge, determined from the in situ experiments.
d
Coloration efficiency is derived from the equation η = δOD781/Q.
e
Decay of coloration efficiency after cyclic scans.
SI-5
decay (%)e
0
0
1.20
1.81
2.41
3.01
3.01
3.01
3.61
3.61
4.82
O 2N
O
NO2
N
H
O2N
N
H
O
NO2
N
N
OMe
OMe
H2 N
O
NH2
N
N
OMe
OMe
Figure S1. IR spectra of (a) compound 1, (b) compound 2 and (c) monomer 3.
SI-6
O2 N 8
1 O
7
6
5 N 4 3
2
NO2
a
b
H
(a)
N
H
d
c
(b)
Figure S2. (a) 1H NMR and (b) 13C NMR spectra of compound 1 in DMSO-d6.
SI-7
O2N 8
1 O
7
6
5 N 4
3
9
10
11
2
NO2
a
N
b
e
f
c
d
12
OMe
OMe
(a)
(b)
Figure S3. (a) 1H NMR and (b) 13C NMR spectra of compound 2 in DMSO-d6.
SI-8
O2N 8
1 O
7
6
5 N 4
3
9
10
2
11
NO2
a
N
b
e
f
c
d
12
OMe
OMe
Figure S4. H-H COSY and C-H HMQC spectra of compound 2 in DMSO-d6.
SI-9
1 O
H2N 8
7
6
5 N 4
3
9
10
11
2
NH2
a
N
b
e
f
c
d
12
OMe
OMe
(a)
(b)
Figure S5. (a) 1H NMR and (b) 13C NMR spectra of monomer 3 in DMSO-d6.
SI-10
1 O
H2N 8
7
6
5 N 4
3
9
10
2
11
NH2
a
N
b
e
f
c
d
12
OMe
OMe
Figure S6. H-H COSY and C-H HMQC spectra of monomer 3 in DMSO-d6.
SI-11
O H
N
H O
N
O
N
N
OMe
OMe
O
n
Figure S7. IR spectrum (film) of polyamide Ib.
SI-12
O H
N 8
H O
N
1 O
7
6
5 N 4
3
9
10
11
2
a
N
b
e
f
13
16
g
h
O
15
14
n
c
d
12
OMe
OMe
(a)
(b)
Figure S8. (a) 1H NMR and (b) 13C NMR of polyamide Ib in DMSO-d6.
SI-13
O H
N
H O
N
O
N
N
OMe
OMe
O
n
Figure S9. Typical TGA curves of polyamide Ib.
SI-14
O H
N
H O
N
O
N
N
OMe
OMe
O H
N
H O
N
O
N
N
OMe
OMe
O H
N
n
O
H O
N
O
N
N
OMe
OMe
Figure S10. DSC curves of polyamide Ia, Ib and Ic.
SI-15
n
F3C
CF3
n
Figure S11. Electrochromic behavior by increasing the applied voltage to 1.10 (V vs.
Ag/AgCl) of polyamide Ib thin film (~70 nm in thickness) on the ITO-coated glass substrate
in 0.1 M TBAP/CH3CN.
SI-16
Figure S12. Calculation of optical switching time at 781 nm at the applied potential, and
current-time curves of polyamide Ib thin film (~80 nm in thickness) on the ITO-coated glass
substrate (coated area: 1.6 cm x 0.6 cm) in 0.1 M TBAP/CH3CN.
SI-17