Polym. Bull.

(2016) 73:2427–2438
DOI 10.1007/s00289-016-1670-y

ORIGINAL PAPER

Synthesis, characterization and electrochromic

properties of polyamides having triphenylamine
derivatives

Myung Jun Lee1 • Young Jun Kwak1 •

Woong Chul Seok1 • Seung Woo Lee1

Received: 2 October 2015 / Revised: 20 March 2016 / Accepted: 15 April 2016 /

Published online: 22 April 2016
Ó Springer-Verlag Berlin Heidelberg 2016

Abstract Three diamine monomers with methoxy group substituents in the ortho,
meta and para positions in the triphenylamine moiety were synthesized by a
nucleophilic aromatic substitution reaction using 4-fluoronitrobenzene with o-, m-
and p-anisidine, respectively. From these diamine monomers, electrochromic
polyamides were synthesized by a direct polycondensation reaction. 1H nuclear
magnetic resonance and Fourier transform infrared spectroscopy confirmed the
synthesis of the electrochromic polyamides. The measured inherent viscosity of the
polyamides was in the range 0.65–0.78 dL/g. All the polyamides showed good
thermal properties and formed good spin-coated thin films. The energy band gap
and oxidation onset potential, Eonset, for the polyamide films was in the order of
tere-p-OCH3TPA polyamide \ tere-o-OCH3TPA polyamide \ tere-m-OCH3TPA
polyamide. The electrical properties and spectroelectrochemical behavior varied
according to the methoxy substituted position in the triphenylamine moiety.

Keywords Electrochromic polyamides  Methoxy substituted triphenylamine

derivatives  Electrochromism  Oxidative polyamides  Spectroelectrochemical
properties

Introduction

Electrochromism is defined as a reversible color change in materials caused by the

passing of a current or the application of a potential [1–6]. Electrochromic materials
have attracted considerable attention in both academia and industry because of their
potential application, such as reflectance mirrors, sunglasses, controllable aircraft

& Seung Woo Lee

leesw1212@ynu.ac.kr
1
School of Chemical Engineering, Yeungnam University, 280 Daehak-ro, Gyeongsan 712-749,
Republic of Korea

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canopies, smart windows, and electrochromic displays [3, 6, 7]. A variety of

electrochromic materials have been reported [2, 4, 5, 8–10]: (1) transition metal
oxides, such as WO3; (2) small molecular dyes including organic or inorganic, such
as viologens and Prussian blue; (3) conducting polymers, such as polyanilines,
polypyrroles and polythiophenes, and (4) oxidizable organic polymers with
triphenylamine derivatives.
Among the electrochromic materials, oxidizable organic polymers containing
triphenylamine derivatives have attracted considerable interest because tripheny-
lamine derivatives can be oxidized easily in the nitrogen center to form a
stable cationic radical, and the oxidation process is always associated with a
noticeable change in coloration [11, 12]. Moreover, the electrochemical properties,
such as the band gap, color change and response time of triphenylamine derivatives,
can be controlled by adjusting the incorporated substituent’s position and
introducing side groups. Therefore, many electrochromic polymers, such as
polyimide and polyamide, containing triphenylamine derivatives have been
investigated to apply hole transporting materials in thin layer electro-optical
devices, such as organic light-emitting diodes, solar cells and organic field effect
transistors [7, 13–19].
The anodic oxidation mechanism of triphenylamine derivatives has been well
studied. The cationic radical generated by applying a voltage is unstable and the
cationic radical can resonance to the ortho and para position of the aromatic ring in
the triphenylamine moiety [15, 20–24]. On the other hand, most reported oxidation
mechanisms of polymers with triphenylamine derivatives have been studied using
polymers containing the para position substituted triphenylamine moiety. To
examine the effects of the substituted position in triphenylamine derivatives, three
diamine monomers with methoxy group substituents in the ortho, meta and para
positions in the triphenylamine moiety were synthesized. For this study, the
electrochromic polyamides were synthesized by a direct polycondensation reaction
using the synthesized diamines and terepthalic acid. The chemical structures and
thermal properties of the polyamides were characterized using spectroscopic
techniques. The optical properties and electrochemical behaviors were examined
from the polyamide films.

Experimental

Materials

The materials, p-anisidine (TCI), m-anisidine (TCI), o-anisidine (TCI), potassium

permanganate (Aldrich), 4-fluoronitrobenzene (from Alfa Aesar), cesium fluoride
(Aldrich), hydrazine monohydrate (Aldrich), terephthalic acid (Aldrich), triphenyl
phosphite (Aldrich), tetrabutylammonium perchlorate (TPBA), and 10 % palladium
on activated carbon (Aldrich) were used as received. The solvents, dimethyl
sulfoxide (DMSO), dimethyl acetamide (DMAc), ethanol, and pyridine (Py), were
purchased from Aldrich and used as received. The solvent for polymerization, N-

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methyl-2-pyrrolidinone (NMP), was obtained from Aldrich, purified by distillation

over calcium hydride and stored over 4 Å molecular sieves.

Synthesis of the diamine monomers

A diamine monomer with a triphenylamine moiety containing a p-methoxy

substituent, 4,40 -diamino-400 -methoxytriphenylamine (p-OCH3TPA), was synthe-
sized using a two-step chemical reaction (Scheme 1). First, 4,40 -dinitro-400 -
methoxytriphenylamine was prepared from p-anisidine (2.5 g, 20.3 mmol), 4-flu-
oronitrobenzene (6.30 g, 44.6 mmol) and cesium fluoride (6.78 g, 44.6 mmol)
dissolved in dried 100 mL DMSO, and stirred at 150 °C for 24 h (Scheme 1). The
reaction mixture was poured into cold water, resulting in the precipitation of an
orange-colored solid, which was collected by filtration and washed with methanol
[25, 26]. The yield of 4,40 -dinitro-400 -methyltriphenylamine (DN-p-OCH3TPA) was
5.71 g (70 %); 1H NMR (DMSO-d6, ppm): 3.67 (s, Ar-OCH3, 3H), 7.03–7.06 (d,
Ar–H, 2H), 7.13–7.16 (d, Ar–H, 4H), 7.18–7.21 (d, Ar–H, 2H), 8.12–8.15 (d, Ar–H,
4H).
In the same manner, 4,40 -dinitro-300 -methoxytriphenylamine (DN-m-OCH3TPA)
and 4,40 -dinitro-200 -methoxytriphenylamine (DN-o-OCH3TPA) were prepared from
a reaction of 4- fluoronitrobenzene with m-anisidine and o-anisidine, respectively.
The yield of DN-m-OCH3TPA was 57 %; 1H NMR (DMSO-d6, ppm): 3.75 (s, Ar-
OCH3, 3H), 6.81–6.83 (t, Ar–H, 2H), 6.94–6.97 (m, Ar–H, 1H), 7.20–7.23 (d, Ar–
H, 4H), 7.39–7.45 (t, Ar–H, 1H), 8.17–8.20 (d, Ar–H, 4H). The yield of DN-o-

Scheme 1 Synthesis route and chemical structures of 4,40 -diamino-200 -methoxytriphenylamine

(o-OCH3TPA), 4,40 -diamino-300 -methoxytriphenylamine (m-OCH3TPA), 4,40 -diamino-400 -methoxyt-
riphenylamine (p-OCH3TPA) and polyamides with terephthalic acid

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OCH3TPA was 65 %; 1H NMR (DMSO-d6, ppm): 3.65 (s, Ar-OCH3, 3H),

7.03–7.08 (d, Ar–H, 1H), 7.10–7.13 (d, Ar–H, 4H), 7.22–7.29 (d, Ar–H, 2H),
7.41–7.47 (t, Ar–H, 1H), 8.12–8.15 (d, Ar–H, 4H).
In the second step, a diamine monomer was prepared from the reduction of
dinitro groups using Pd–C as the reducing agent. A mixture of 5.0 g (13.7 mmol) of
DN-p-OCH3TPA, 2.52 g (38.3 mmol) of hydrazine monohydrate, 0.2 g of 10 %
Pd–C, and 100 ml of ethanol was stirred at 120 °C for 8 h (Scheme 1). The reaction
mixture was filtered through Celite to remove the Pd–C, and the filtrate was added
to 100 ml of water to obtain precipitates, which were filtered and dried [25, 26]. The
crude product was recrystallized from ethanol. The product yield was 3.80 g
(91 %); 3.67 (s, Ar-OCH3, 3H), 4.72 (s, Ar-NH2, 4H), 6.47–6.50 (d, Ar–H, 2H),
6.67–6.70 (d, Ar–H, 4H), 6.68–6.71 (d, Ar–H, 6H).
In the same manner, 4,40 -diamino-300 -methoxytriphenylamine (m-OCH3TPA)
and 4,40 -diamono-200 -methoxytriphenylamine (o-OCH3TPA) were prepared from
the reduction of DN-m-OCH3TPA and DN-o-OCH3TPA, respectively. The yield of
m-OCH3TPA was 84 %; 1H NMR (DMSO-d6, ppm): 3.58 (s, Ar-OCH3, 3H), 4.99
(s, Ar-NH2, 4H), 6.11–6.12 (s, Ar–H, 1H), 6.17–6.24 (q, Ar–H, 2H), 6.53–6.58 (d,
Ar–H, 4H), 6.79–6.83 (d, Ar–H, 4H), 6.94–6.98 (t, Ar–H, 1H). The yield of o-
OCH3TPA was 90 %; 1H NMR (DMSO-d6, ppm): 3.57 (s, Ar-OCH3, 3H), 4.56 (s,
Ar-NH2, 4H), 6.43–6.46 (s, Ar–H, 4H), 6.52–6.55 (d, Ar–H, 4H), 6.83–6.92 (m, Ar–
H, 2H), 6.96–7.07 (m, Ar–H, 2H).

Preparation of polyamides

The polyamides were prepared from a direct polycondensation reaction using

terephthalic acid and the prepared diamine monomers. For example, tere-p-
OCH3TPA polyamide was synthesized as follows [27, 28]. A mixture of
terephthalic acid acid (1.00 g, 6.02 mmol), p-OCH3TPA (1.85 g, 6.02 mmol),
50 mL of NMP/Py (v/v = 4/1), and triphenyl phosphite (4.10 g, 13.24 mmol) was
stirred at room temperature under nitrogen for 2 h. The reaction mixture was heated
to 100 °C for an additional 12 h. Subsequently, the reaction solution was poured
into hot methanol with vigorous stirring, producing tere-p-OCH3TPA polyamide as
a powder precipitate in 92 % yield. In the same manner, tere-m-OCH3TPA and tere-
o-OCH3TPA polyamide were synthesized using m-OCH3TPA and o-OCH3TPA
instead of p-OCH3TPA, respectively.

Measurements

The 1H nuclear magnetic resonance (NMR, Bruker AM 300) spectra were obtained
at room temperature. The Fourier transform infrared (FTIR, Nicolet 6700, Thermo
scientific) spectra were collected on a spectrometer equipped with a Diamond ATR
system. The ultraviolet–visible (UV–vis) absorption spectra were obtained using an
UV–vis spectrophotometer (UV-1800, Shimadzu). The glass transition temperatures
were measured over the temperature range 25–250 °C, by differential scanning
calorimetry (DSC, model DSC-60C, Shimadzu). The degradation temperatures were
measured over the temperature range 50–800 °C, by thermogravimetric analysis

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(TGA, model DTG-60, Shimadzu). For the DSC and TGA measurements, a ramp
rate of 10.0 °C/min and a flow rate of 100 cc/min dry nitrogen gas were used.
Cyclic voltammetry (Epsilon) was performed using a three-electrode cell with
indium tin oxide (ITO, the polymer film area was ca. 0.5 9 1.1 cm2) as the working
electrode. The polyamide films on ITO substrates were produced by a conventional
spin casting method using 2.0 wt% solutions in DMAc. These films were then dried
at 120 °C for 12 h under a nitrogen atmosphere. The electrochemical cell was
composed of a 1 cm cuvette with ITO as the working electrode, platinum wire as the
auxiliary electrode and Ag/AgCl as the reference electrode.

Results and discussion

Three types of diamine with a triphenylamine moiety having a methoxy substituent

in different positions were synthesized via a nucleophilic aromatic substitution
reaction and a subsequent reduction reaction of the dinitro groups. The synthesized
diamines, p-OCH3TPA, m-OCH3TPA and o-OCH3TPA, were characterized by 1H
NMR spectroscopy (Fig. 1). The spectra of the synthesized diamines showed the
characteristic singlet chemical shifts in the range 3.50–3.70 ppm, and a multiplet
chemical shift in the range 6.00–7.20 ppm, for the 3 protons from the methoxy
group and 12 protons of the aromatic ring, respectively, independent of the
substituted position. Moreover, singlet chemical shifts in the range 4.50–5.00 ppm,

Fig. 1 1H NMR spectra of a 4,40 -diamino-200 -methoxytriphenylamine (o-OCH3TPA), b 4,40 -diamino-

300 -methoxytriphenylamine (m-OCH3TPA) and c 4,40 -diamino-400 -methoxytriphenylamine (p-OCH3TPA)
in dimethyl-d6 sulfoxide (DMSO-d6)

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were assigned to the proton of the amine groups. The results of the three measured
1
H NMR spectra were in accordance with the expected chemical structure.
Polyamides with triphenylamine moiety containing a methoxy substituent at
different positions were synthesized using terephthalic acid and OCH3TPA diamine
monomers from direct polycondensation, modifying the procedure reported
previously (see Scheme 1) [27–29]. The obtained polymers were characterized by
1
H NMR. Figure 2 presents the 1H NMR spectrum of the synthesized polyamides.
The synthesized diamine monomers had a characteristic proton peak for amine
groups in the range 4.50–5.00 ppm, while the synthesized polyamides did not show
any proton peak originating from the amine groups of the p-, m-, o-OCH3TPA
monomers. After polymerization, a new singlet peak appeared in the range of
10.2–10.6 ppm, which was assigned to the proton of the amide groups from the
reaction of a carboxylic acid group and amine group. In addition, no unreacted
carboxylic acid or amine from the characteristic chemical shift in terephthalic acid
and diamine monomers were detected in the 1H NMR spectra of the polyamides.
The measured inherent viscosity of the polyamides in NMP at 25 °C using an
Ubbelhode-type viscometer was in the range 0.65–0.78 dL/g. The 1H NMR spectra
and inherent viscosity suggest that the polyamides had been synthesized success-
fully with a reasonably high molecular weight. In addition, the solubility of the
polymers was qualitatively checked in several solvents. All the polyamides showed

Fig. 2 1H NMR spectra of a tere-o-OCH3TPA polyamide, b tere-m-OCH3TPA polyamide and c tere-o-

OCH3TPA polyamide in dimethyl-d6 sulfoxide (DMSO-d6)

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good solubility in polar aprotic solvents such as NMP, DMSO, DMAc and N,N-
dimethylformamide, but they were insoluble in nonpolar solvents.
The obtained polyamides were evaluated by FT-IR spectroscopy (Fig. 3). The
polyamide films showed characteristic bands at 1654, 1590, 1525, and 1240 cm-1,
regardless of the substituted position of the methoxy group in the triphenylamine
moiety [28]. In Fig. 3, the characteristic bands assigned to the stretching vibration
of the C=O group (amide I) and the in-plane bending vibration of the NH group
(amide II) in the amide unit of the main chain were detected at 1654 and
1525 cm-1, respectively. The characteristic bands of the triphenylamine moiety
were observed at 1590 cm-1. In addition, the characteristics bands of the substituted
C–O stretching vibration for methoxy groups were detected at 1240 and 1050 cm-1
[15]. FT-IR spectroscopy confirmed that polyamides with a triphenylamine moiety
containing a methoxy substituted in various positions had been synthesized
successfully. In addition, the thermal properties of the polyamides were determined
(Table 1).
The optical properties of the polyamide films were investigated by UV–vis
spectroscopy. The energy band gap (i.e., the difference between the highest
occupied molecular orbital (HOMO) level and lowest unoccupied molecular orbital
(LUMO)) of the polyamide films were determined using the konset value from the
measured UV–vis spectra. The estimated band gap for tere-p-OCH3TPA polyamide,
tere-m-OCH3TPA polyamide and tere-o-OCH3TPA polyamide was 2.72, 2.84 and
2.82 eV, respectively. The calculated energy band gap for the polyamide films was
in the order of tere-p-OCH3TPA polyamide \ tere-o-OCH3TPA polyamide \ tere-
m-OCH3TPA polyamide. This suggests that the position of the methoxy substituent
affects the energy band gap of the triphenylamine moiety.

Fig. 3 FT-IR spectra of the synthesized polyamide films: (a) tere-o-OCH3TPA polyamide, (b) tere-m-
OCH3TPA polyamide and (c) tere-p-OCH3TPA polyamide

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Table 1 Inherent viscosity, glass transition temperatures (Tg), and decomposition temperatures (Td) of
the polyamides
Sample designation Inherent viscositya Tg (°C)b Td (°C)c

tere-o-OCH3TPA 0.65 235 413

tere-m-OCH3TPA 0.66 231 419
tere-p-OCH3TPA 0.78 238 407
a
Measured in DMAc at a concentration of 0.5 g/dL at room temperature
b
Measured by DSC with a heating rate of 10.0 °C/min
c
Determined by TGA at a heating rate of 10.0 °C/min under a nitrogen atmosphere: Td = temperature of
5.0 % weight loss

The electrochemical behavior of the polyamides was examined by CV of the

coated film on the ITO-coated glass substrates as the working electrode in
acetonitrile containing 0.1 M of TBAP as an electrolyte. Figure 4 presents the
typical CVs of the polyamide films. From CV analysis, the estimated oxidation
onset potential, Eonset, for tere-p-OCH3TPA polyamide, tere-m-OCH3TPA poly-
amide and tere-o-OCH3TPA polyamide was 0.55, 0.66 and 0.61 eV, respectively.
The measured Eonset for the polyamide films was in the order of tere-p-OCH3TPA
polyamide \ tere-o-OCH3TPA polyamide \ tere-m-OCH3TPA polyamide. This
might be due to radical cation stabilization by the incorporation of an electron
donating group in the para and ortho position. The electrogenerated cationic radical
of triphenylamine is unstable and the cationic radical could resonance to the ortho
and para position [21]. Moreover, the HOMO and LUMO of the polyamide films
were determined, based on the external ferrocene/ferrocenium (Fc/Fc?) redox
standard half-wave potential (E1/2) in acetonitrile using an Ag/AgCl electrode.

Fig. 4 CV responses of (a) tere-o-OCH3TPA polyamide, (b) tere-m-OCH3TPA polyamide and (c) tere-
p-OCH3TPA polyamide films coated on indium tin oxide glass substrates in acetonitrile containing 0.1 M
tetrabutylammonium perchlorate

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Table 2 Redox potentials and energy levels of the polyamides

Sample Thin film (nm) Oxidation potential Eg (eV)b HOMO (eV)c LUMO (eV)
(V)a

kmax konset E1/2 Eonset

tere-o-OCH3TPA 377 440 0.68 0.61 2.82 4.99 2.17

tere-m-OCH3TPA 350 437 0.69 0.66 2.84 5.04 2.20
tere-p-OCH3TPA 377 456 0.57 0.55 2.72 4.93 2.21
a
Measured by cyclic voltammograms (CV) versus Ag/AgCl in acetonitrile containing 0.1 M tetra-
butylammonium perchlorate. E1/2 Oxidation half-wave potential from CV
b
Calculated from polyimide films by the equation: Eg (energy band gap between HOMO and
LUMO) = 1240/konset
c
Calculated from E1/2 of CV. This value were referenced to ferrocene (4.8 eV)

Table 2 lists the HOMO and LUMO of the polyamide films determined from the
half-wave potentials and the onset absorption wavelength of the polymer films,
respectively. The differences between the band gaps and HOMO levels of the
polyamide films might be due to differences in their substituted methoxy group
position in the triphenylamine moiety. The different chemical structures of the
triphenylamine moiety affects the electronic structure of triphenylamine in the
polyamide backbones upon the application of a voltage potential.
The optical characteristics of the electrochromic polyamide films were
determined by UV–vis spectroscopy while applying a voltage potential using
CV. The experimental conditions were the same as those used for CV. Figure 5
presents the spectroelectrochemical results using UV–vis spectroscopy for tere-
p-OCH3TPA, tere-m-OCH3TPA and tere-o-OCH3TPA polyamide films. In the
neutral state, tere-p-OCH3TPA, tere-m-OCH3TPA and tere-o-OCH3TPA poly-
amide films showed strong absorption at wavelengths around 377, 350 and
377 nm, respectively, which is characteristic of the triphenylamine moiety, but
were almost transparent in the visible region, regardless of the chemical structure
of the triphenylamine moiety. With increasing applied voltage, the strong
absorption peak at 377 nm decreased gradually while a new peak at 540 and
860 nm appeared in the visible region, which increased in intensity for the tere-
p-OCH3TPA polyamide film. In addition, the absorption peak at 377 nm
decreased gradually while new peak at 573 and 790 nm in the visible region
increased abruptly in intensity with increasing applied voltage for the tere-o-
OCH3TPA polyamide film. The appearance and growth of the new peaks was
attributed to the formation of a resonance-stabilized cationic radical of the ortho
and para position methoxy group substituted TPA moiety by applying a positive
potential. On the other hand, the absorption peak at 350 nm decreased gradually
while a new peak at 850 nm increased by applying a potential, and the intensity of
the new appearance peak is very weak for the tere-m-OCH3TPA polyamide film.
The spectroelectrochemical behavior of tere-m-OCH3TPA polyamide film was
different from that of tere-p-OCH3TPA and tere-o-OCH3TPA polyamide film.

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Fig. 5 Spectroelectrochemical behavior at the applied potentials of a tere-o-OCH3TPA polyamide, b tere-m-OCH3TPA polyamide and c tere-p-OCH3TPA polyamide
films coated on indium tin oxide glass substrates in acetonitrile containing 0.1 M tetrabutylammonium perchlorate
Polym. Bull. (2016) 73:2427–2438
Polym. Bull. (2016) 73:2427–2438 2437

These results may come from the no resonance-stabilized cationic radical

formation for the meta position methoxy group substituted triphenylamine moiety.

Conclusions

Three types of electroactive diamine monomers with a methoxy group substituted in

the ortho, meta and para positions of triphenylamine, p-OCH3TPA, m-OCH3TPA
and o-OCH3TPA were synthesized by a nucleophilic aromatic substitution reaction.
Electroactive polyamides were synthesized by direct polycondensation from a
reaction between the electroactive diamine monomers and terephthalic acid. All the
polyamides were synthesized and produced good spin-coated thin films. The
oxidation onset potential for tere-p-OCH3TPA polyamide, tere-m-OCH3TPA
polyamide and tere-o-OCH3TPA polyamide was 0.55, 0.66 and 0.61 eV, respec-
tively. The HOMO, LUMO and band gap of the polyamides varied according to the
substituted methoxy group position in the triphenylamine moiety. The spectroelec-
trochemical behavior of the polyamides showed a difference according to the
chemical structure of the diamines and applied voltage.

Acknowledgments This study was supported by the Basic Science Research Program through the
National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and
Technology (NRF-2015R1D1A3A01019009).

References
1. Peter B, Michael HG (2010) Chromic phenomena; technological applications of colour chemistry.
Royal Society of Chemistry, Cambridge
2. Mortimer RJ (2011) Electrochromic materials. Annu Rev Mater Sci 41:241–268
3. Yen H-J, Liou G-S (2010) Novel blue and red electrochromic poly(azomethine ether)s based on
electroactive triphenylamine moieties. Org Electron 11:299–310
4. Abidin T, Zhang Q, Wang K-L, Liaw D-J (2014) Recent advances in electrochromic polymers.
Polymer 55:5293–5304
5. Mortimer RJ (1997) Electrochromic materials. Chem Soc Rev 26:147–156
6. Rosseinsky DR, Mortimer RJ (2001) Electrochromic systems and the prospects for devices. Adv
Mater 13(11):783–793
7. Wang H-M, Hsaio S-H (2009) Electrochemically and electrochromically stable polyimides bearing
tert-butyl-blocked N,N,N0 ,N0 -tetraphenyl-1,4-phenylenediamine units. Polymer 50:1692–1699
8. Liu S, Kurth DG, Mohwald H, Volkmer DA (2002) A thin-film electrochromic device based on a
polyoxometalate cluster. Adv Mater 14:225–228
9. Zhang T, Liu S, Kurth DG, Faul CFJ (2009) Organized nanostructured complexes of polyoxomet-
alates and surfactants that exhibit photoluminescence and electrochromism. Adv Funct Mater
19:642–652
10. Maier A, Rabindranath AR, Tieke B (2009) Fast-switching electrochromic films of zinc polyimi-
nofluorene-terpyridine prepared upon coordinative supramolecular assembly. Adv Mater 21:959–963
11. Hsiao S-H, Liou G-S, Kung Y-C, Lee Y-J (2010) Synthesis and characterization of electrochromic
poly(amide-imide)s based on the diimide-diacid from 4,40 -diamino-400 -methoxytriphenylamine and
trimellitic anhydride. Eur Polym J 46:1355–1366
12. Hsiao S-H, Liou G-S, Kung Y-C, Yen H-J (2008) High contrast ratio and rapid switching elec-
trochromic polymeric films based on 4-dimethylamino)triphenylamine-functionalized aromatic
polyamides. Macromolecules 41(8):2800–2808

123
2438 Polym. Bull. (2016) 73:2427–2438

13. Hsiao S-H, Liou G-S, Wang H-M (2009) Highly stable electrochromic polyamides based on N,N-
bis(4-aminophenyl)-N0 ,N0 -bis(4-tert-butylphenyl)-1,4-phenylene-diamine. J Polym Sci Part A Polym
Chem 47:2330–2343
14. Chung CL, Lee W-F, Lin C-H, Hsiao S-H (2009) Highly soluble fluorinated polyimides based on an
asymmetric bis(ether amine): 1,7-bis(4-amino-2- trifluoromethylphenoxy) naphthalene. J Polym Sci
Part A Polym Chem 47:1756–1770
15. Chang C-W, Liou G-S, Hsiao S-H (2007) Highly stable anodic green electrochromic aromatic
polyamides: synthesis and electrochromic properties. J Mater Chem 17:1007–1015
16. Yen HJ, Guo SM, Yeh JM, Liou G-S (2011) Triphenylamine-based polyimides with trimethyl
substituents for gas separation membrane and electrochromic applications. J Polym Sci Part A:
Polym Chem 49:3637–3646
17. Huang LT, Yen HJ, Liou G-S (2011) Substituent effect on electrochemical and electrochromic
behaviors of ambipolar aromatic polyimides based on aniline-derivatives. Macromolecules
44:9595–9610
18. Hsiao S-H, Liou GS, Kung Y-C, Hsiung T-J (2010) Synthesis and properties of new aromatic
polyamides with redox-active 2,4-dimethoxytriphenylamine moieties. J Polym Sci Part A Polym
Chem 48:3392–3401
19. Iwan A, Sek D (2011) Polymers with triphenylamine units: photonics and electroactive materials.
Prog Polym Sci 36:1277–1325
20. Yeh SJ, Tasi CY, Huang C-Y, Liou G-S, Cheng S-H (2003) Electrochemical characterization of
small organic holetransport molecules based on the triphenylamine unit. Electrochem Commun
5:373–377
21. Yen H-J, Gou S-M, Liou G-S (2010) Synthesis and unexpected electrochemical behavior of the
triphenylamine-based aramids with ortho- and para-trimethyl-protective substituents. J Polym Sci
Part A Polym Chem 48:5271–5281
22. Kuorosawa T, Chueh C-C, Liu C-L, Higashihara T, Ueda M, Chen W-C (2010) High performance
volatile polymeric memory devices based on novel triphenylamine-based polyimides containing
mono-or dual-mediated phenoxy linkages. Macromolecules 43(3):1236–1244
23. Otero L, Sereno L, Fungo F, Liao Y-L, Lin C-Y, Wong K-T (2006) Synthesis and properties of a
novel electrochromic polymer obtained from the electropolymerization of a 9,90 -spirobifluorene-
bridged donor–acceptor (D–A) bichromophore system. Chem Mater 18(15):3495–3502
24. Seo ET, Nelson RF, Fritsch JM, Marcoux LS, Leedy DW, Adams RN (1966) Anodic oxidation
pathways of aromatic amines. Electrochemical and electron paramagnetic resonance studies. J Am
Chem Soc 88(15):3498–3503
25. Lee SH, Bae J, Seo HM, Im JH, Shin HS, Yoo EJ, Lee SW (2014) Electrochromism properties of
polyimides possessing triphenylamine moieties with different substituents. Mol Cryst Liq Cryst
598:6–15
26. Shin HS, Yoo EJ, Lee MJ, Seok WC, Lee SW (2015) Electrochromic properties of polyimides
prepared from methyl substituted triphenylamine moiety with different dianhydrides. J Nanoelectron
Optoelectron 10:498–503
27. Bae J, Chae B, Seo HM, Jung YM, Lee SW (2014) Structural characterization of triphenylamine
(TPA)-based polymers during the oxidative reaction by two-dimensional (2D) infrared correlation
study. J Mol Struct 1069:200–204
28. Choi KH, Lee KH, Jung JC (2001) Synthesis of new poly(amide imide)s with (n-alkyloxy)phenyloxy
side branches. J Polym Sci Part A Polym Chem 39:3818–3825
29. Higashi F, Goto M, Nakano Y, Kakinoki H (1980) Wholly aromatic polyamides by the direct
polycondensation reaction using triphenyl phosphite in the presence of poly(4-vinylpyridine).
J Polym Sci Part A Polym Chem 18:851–856

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