Synthetic Metals 220 (2016) 147154

Contents lists available at ScienceDirect

Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Synthesis and characterisation of azobenzene-bridged cationic

cationic and neutralcationic electrochromic materials
Cheng-bin Gong, Li-hua He, Jun-fei Long, Lan-Tao Liu, Song Liu, Qian Tang* , Xiang-kai Fu
The Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing,
400715, China

A R T I C L E I N F O

Article history:
Received 30 March 2016
Received in revised form 30 May 2016
Accepted 9 June 2016
Available online 22 June 2016
Keywords:
Electrochromic materials
Electrochromic devices
Azobenzene
Aromatic esters
Pyridinium salts

A B S T R A C T

Azobenzene-bridged cationicneutral and cationiccationic were synthesized, characterized and

compared with azobenzene-bridged neutralneutral materials. Azobenzene-bridged cationiccationic
and neutralneutral materials exhibited well-dened and reversible redox couples during redox
processes, good electrochromic behavior, and appropriate contrast ratios in the visible regions. However,
azobenzene-bridged cationicneutral materials exhibited a quasi-reversible electrochemical process.
The electrochromic stability of these compounds is in the order: azobenzene-bridged neutralneutral
materials > azobenzene-bridged cationiccationic materials > azobenzene-bridged cationicneutral
materials. Electrochromic devices based on azobenzene-bridged neutralneutral materials achieved
maximum optical contrast, fast response time, and high coloration efciency. The substituents of
azobenzene-bridged cationiccationic materials and the anions of azobenzene-bridged cationicneutral
materials did not signicantly inuence their electrochemical properties and response time, but slightly
affected the maximum optical contrast, change in optical density, and coloration efciency.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Electrochromic materials (ECMs) refer to materials that
undergo optical changes due to electrochemical reaction [1,2].
Electrochromic devices (ECDs), which are based on ECMs, have
potential applications in smart windows [36], electrochromic
displays [7,8], ink-jet printers [9], earth-tone chameleon materials
[10,11], and anti-glare rear-view mirrors for cars [12,13]. Consequently, ECMs have attracted extensive research attention from
researchers since Platt [14] reported the electrochromic phenomenon in dyes. ECMs include inorganic materials, such as metal
oxides [1518], and organic materials, such as phenothiazine
[1924], anthraquinone [2532], viologen [3336], thiophene
[3740], polythiophene [4147], polyaniline [4850], polypyrrole
[5154], and polyimide [55]. Compared with inorganic ECMs,
organic ECMs exhibit the unique advantages of high optical
contrast, fast switching speed, exible device fabrication, and a
multitude of achievable colors via chemical structure variation.
Azobenzene and its derivatives comprise a dominant class of
synthetic colorants that demonstrate the advantages of bright
colors, good stability, low ammability, and reversible

photoisomerization [56,57]. Aromatic esters have been reported

to display electrochromic properties through the formation of
anionic radicals via electrochemical reduction [5862]. Dicationic
pyridinium salts, such as the viologens, are extensively used in
electrochromic applications by reducing bleached dicationic
pyridinium salts into colored monocationic pyridinium salts,
and subsequently, into a neutral state [63,64]. Azobenzene-bridged
neutralneutral materials are reported to display good electrochromic properties [60,61]. In this work, azobenzene-bridged
cationicneutral materials (compounds 1ad) and cationic
cationic materials (compounds 2ac) (Scheme 1) were synthesised, and their electrochromic and photoresponsive properties
were investigated and compared with azobenzene-bridged
neutralneutral materials. The inuences of the substituents of
compounds 1ad and the anions of compounds 2ac were also
studied.
2. Experimental
2.1. Materials and instrumentation
All chemical reagents were purchased from Aladdin Co.,
Shanghai, China, and used as received. All solvents were of

* Corresponding author.
E-mail address: qiantang@swu.edu.cn (Q. Tang).
http://dx.doi.org/10.1016/j.synthmet.2016.06.011
0379-6779/ 2016 Elsevier B.V. All rights reserved.

148

C.- Gong et al. / Synthetic Metals 220 (2016) 147154

Scheme 1. Chemical structures of compounds 1ad and 2ac.

analytical-reagent grade, commercially available, and used without further purication.

1
H NMR and 13C NMR spectra were measured with a Bruker AV
600 (600 MHz) spectrometer at 298 K using tetramethylsilane as
the internal standard. Ultravioletvisible (UVvis) spectra were
obtained with a UV-4802 spectrophotometer [UNICO (Shanghai)
Instruments Co. Ltd., China]. Cyclic voltammetry (CV) was
performed on a CHI 650 B electrochemical workstation using a
three-electrode system. Ag/AgCl was used as the reference
electrode. High performance liquid chromatography-Mass spectra
were performed on a Bruker Esquire 2000 HCT LC/MS system.
Melting points were measured on a SGWX-4 melting point
apparatus (Shanghai Yidianwuliguangxue Instrument Co., Ltd.).
Elemental analysis was performed by an Elementar Vario Micro
Select (Germany). Fourier transform infrared spectra (FT-IR,
4004000 cm
1) were recorded on a Perkin-Elmer Model GX
spectrometer (USA) via the KBr pellet method.
2.2. General synthesis of cationicneutral materials (compounds
1a-d)
The synthetic route of compounds 1a-d is depicted in Scheme 2.
4-(4-Hydroxyphenylazo)pyridine was synthesized according to
the method reported by Lu et al. [65]. 1H NMR (600 MHz, DMSO-d6)

d (ppm): 8.72 (s, 2H, J = 6.0 Hz), 7.92 (d, 2H, J = 8.4 Hz), 7.77 (d, 2H,
J = 3.6  6.0 Hz), 6.97 (d, 2H, J = 9.0 Hz), 4.87 (s, 1H).
R1COCl was synthesized by reuxing R1COOH (126.0 mmol) in
thionyl chloride (20 mL, 0.27 mol) for 6 h, which yielded a clear
yellow solution. Removal of excess thionyl chloride via distillation
yielded the crude product of R1COCl, which was used directly for
the next reaction without further purication.
4-(4-Hydroxyphenylazo)pyridine (5.0 mmol) was dissolved in
dry dichloromethane (10 mL). Triethylamime (2.0 mL, 14.0 mmol)
was added and the mixture cooled in an ice bath, and an ice-cooled
(0  C) solution of R1COCl (8.0 mmol) in dichloromethane (20 mL)
was added dropwise. The resulting solution was mechanically
stirred overnight at room temperature. The solvent was removed
by
rotary
evaporation.
(E)-4-(Pyridin-4-yldiazenyl)phenyl
4-substituted benzoate (compounds 4a-d) was obtained by
recrystallising from methanol.
(E)-4-(Pyridin-4-yldiazenyl)phenyl methacrylate (Compound
4a): orange solid (0.80 g) yielded 59.7%. Mp: 144.0-145.0  C. MS
(ESI): (CH2Cl2, positive mode) m/z: 268.2 (mass = 267.15 g mol
1).
1
H NMR (600 MHz, DMSO-d6) d (ppm): 8.82 (d, 2H, J = 6.0 Hz), 8.03
(d, 2H, J = 8.4 Hz), 7.73 (d, 2H, J = 6.0 Hz), 7.34 (d, 2H, J = 9.0 Hz), 6.40
(s, 1H), 5.83 (s, 1H), 2.09 (s, 3H). 13C NMR (150 MHz, DMSO-d6) d
(ppm): 165.34, 157.40, 154.24, 150.96, 149.95, 135.63, 127.88,
124.81, 122.55, 116.41, 18.34. Elemental analysis calculated (%) for

Scheme 2. Synthetic route for compounds 1ad.

C.- Gong et al. / Synthetic Metals 220 (2016) 147154

C15H13N3O2: C 67.40, H 4.90, N 15.72; found: C 67.29, H 4.83, N

15.76. FT-IR (KBr, cm
1): 3065, 2959, 2925, 1729, 1632, 1582, 1492,
1292, 1204, 1125, 801, 561.
(E)-4-(Pyridin-4-yldiazenyl)phenyl
4-(tert-butyl)benzoate
(Compound 4b): orange solid (0.98 g) yielded 54.1%. Mp:
128.5128.8  C. MS (ESI): (MeOH, positive mode) m/z: 360.3
(mass = 359.22 g mol
1). 1H NMR (600 MHz, DMSO-d6) d (ppm):
8.85 (m, 2H, J = 1.8  6.0 Hz), 8.10 (m, 2H, J = 8.4  17.4 Hz), 7.78 (m,
2H, J = 1.2  6.0 Hz), 7.65 (d, 4H, J = 8.4 Hz), 7.58 (t, 2H, J = 1.8  8.4
Hz), 1.35 (s, 9H). 13C NMR (150 MHz, DMSO-d6) d (ppm): 164.64,
158.03, 157.10, 154.46, 151.94, 150.04, 130.37, 126.35, 125.00, 123.74,
116.41, 35.48, 31.27. Elemental analysis calculated (%) for
C22H21N3O2: C 73.52, H 5.85, N 11.69; found: C 73.38, H 5.94, N
11.78. FT-IR (KBr, cm
1): 3060, 2958, 1735, 1638, 1586, 1261, 1229,
1186, 1061, 837, 730, 564.
(E)-4-(Pyridin-4-yldiazenyl)phenyl nonanoate (Compound 4c):
orange solid (0.91 g) yielded 51.3%. Mp: 68.0-68.5  C. MS (ESI):
(CH2Cl2, positive mode) m/z: 354.3 (mass = 353.2 g mol
1). 1H NMR
(600 MHz, DMSO-d6) d (ppm): 8.82 (d, 2H, J = 5.4 Hz), 8.02 (d, 2H,
J = 9.0 Hz), 7.73 (d, 2H, J = 4.8 Hz), 7.29 (d, 2H, J = 9.0 Hz), 2.60 (t, 2H,
J = 7.8  15.0 Hz), 1.78 (t, 2H, J = 7.2  15.0 Hz), 1.43 (d, 2H, J = 7.8 Hz),
1.35 (t, 2H, J = 7.2  13.8 Hz), 1.30 (t, 8H, J = 5.4  11.4 Hz), 0.90 (t, 3H,
J = 6.6  13.8 Hz). 13C NMR (150 MHz, DMSO-d6) d (ppm): 171.9,
157.44, 154.08, 150.79, 149.88, 124.49, 122.49, 116.43, 50.83, 34.44,
31.85, 29.40, 29.22, 29.09, 24.87, 22.65, 14.07. Elemental analysis
calculated (%) for C21H27N3O2: C 71.40, H 7.70, N 11.89; found: C
71.42, H 7.54, N 11.96. FT-IR (KBr, cm
1): 3034, 2955, 2920, 2850,
1750, 1586, 1494, 1383, 1214, 1151, 856, 563.
(E)-4-(Pyridin-4-yldiazenyl)phenyl 4-(triuoromethyl)benzoate (Compound 4d): golden solid (1.22 g) yielded 63.4%. Mp:
138.0-138.5  C. MS (ESI): (CH2Cl2, positive mode) m/z: 372.2
(mass = 371.19 g mol
1). 1H NMR (600 MHz, DMSO-d6) d (ppm):
8.85 (m, 2H, J = 1.2  6.0 Hz), 8.37 (d, 2H, J = 7.8 Hz), 8.10 (m, 2H,
J = 6.6  8.4 Hz), 8.02 (d, 2H, J = 8.4 Hz), 7.77 (m, 2H, J = 1.8  6.0 Hz),
7.64 (m, 2H, J = 1.8  8.4 Hz). 13C NMR (150 MHz, DMSO-d6) d
(ppm): 163.71, 157.02, 154.10, 152.03, 150.22, 134.14, 133.93, 133.04,
131.29, 126.46, 126.44, 126.42, 125.03, 123.67, 123.24, 116.37, 49.06.
Elemental analysis calculated (%) for C19H12F3N3O2: C 61.46, H 3.26,
N 11.32; found: C 61.40, H 3.39, N 11.20. FT-IR (KBr, cm
1): 3037,
2924, 2853, 1736, 1586, 1496, 1411, 1335, 1279, 1145, 1087, 799, 697,
560.
In a dry 50 mL ask, compounds 4a-d (2.0 mmol), benzyl
bromide or 4-nitrobenzyl bromide (3.0 mmol), and acetonitrile
(20 mL) were charged and then heated to reux for 24 h. The
mixture was then cooled down to room temperature, and the crude
product was obtained via ltration. Compounds 1a-d were
obtained by washing the crude products with diethyl ether

149

followed by recrystallization from ethyl acetate and methanol (4:1,

v:v).
(E)-1-Benzyl-4-((4-(methacryloyloxy)phenyl)diazenyl)pyridin1-ium bromide (Compound 1a): pale brown solid (0.49 g) yielded
68.2%. Mp: 164.0164.5  C. MS (ESI): (MeOH, positive mode) m/z:
358.3 (mass = 358.22 g mol
1). 1H NMR (600 MHz, DMSO-d6) d
(ppm): 9.40 (d, 2H, J = 6.6 Hz), 8.44 (d, 2H, J = 7.2 Hz), 8.13 (d, 2H,
J = 8.4 Hz), 7.57 (t, 4H, J = 9.0  18.0 Hz), 7.47 (t, 3H, J = 7.8  11.4 Hz),
6.35 (s, 1H), 5.98 (s, 1H), 5.95 (s, 2H), 2.04 (s, 3H). 13C NMR
(150 MHz, DMSO-d6) d (ppm): 165.27, 160.99, 155.94, 150.10,
147.83, 135.42, 134.62, 129.52, 126.12, 124.00, 121.03, 63.63, 18.40.
Elemental analysis calculated (%) for C22H20BrN3O2: C 60.28, H
4.60, N 9.59; found: C 60.44, H 4.51, N 9.43. FT-IR (KBr, cm
1): 3104,
2957, 2936, 1730, 1632, 1583, 1455, 1357, 1295, 1207, 1148, 792, 725,
557.
(E)-1-Benzyl-4-((4-((4-(tert-butyl)benzoyl)oxy)phenyl)diazenyl)pyridin-1-ium bromide (Compound 1b): dark red solid
(0.55 g) yielded 61.3%. Mp: 149.5150.5  C. MS (ESI): (MeOH,
positive mode) m/z: 450.4 (mass = 450.29 g mol
1). 1H NMR
(600 MHz, DMSO-d6) d (ppm): 9.40 (d, 2H, J = 6.6 Hz), 8.45 (d,
2H, J = 6.6 Hz), 8.17 (d, 2H, J = 9.0 Hz), 8.10 (d, 2H, J = 8.4 Hz), 7.65 (m,
4H, J = 2.4  11.4 Hz), 7.58 (d, 2H, J = 7.2 Hz), 7.47 (m, 3H, J = 7.2
 11.4 Hz), 5.95 (s, 2H Hz), 1.35 (s, 9H). 13C NMR (150 MHz, DMSOd6) d (ppm): 172.41, 165.24, 156.24, 156.51, 149.42, 146.36, 134.46,
129.94, 128.63, 127.10, 125.68, 124.94, 123.27, 121.64, 61.91, 34.28,
31.36. Elemental analysis calculated (%) for C29H28BrN3O2: C 65.66,
H 5.32, N 7.92; found: C 65.40, H 5.48, N 7.83. FT-IR (KBr, cm
1):
3132, 2946, 2933, 1732, 1634, 1585, 1499, 1461, 1230, 1137, 834, 762,
557.
(E)-1-Benzyl-4-((4-(nonanoyloxy)phenyl)diazenyl)pyridin-1ium bromide (Compound 1c): brick red solid (0.47 g) yielded 51.4%.
Mp: 102.5103.5  C. MS (ESI): (MeOH, positive mode) m/z: 444.4
(mass = 444.28 g mol
1). 1H NMR (600 MHz, DMSO-d6) d (ppm):
9.42 (d, 2H, J = 6.0 Hz), 8.44 (d, 2H, J = 6.0 Hz), 8.13 (d, 2H, J = 8.4 Hz),
7.59 (d, 2H, J = 7.2 Hz), 7.48 (m, 5H, J = 8.4  26.4 Hz), 5.96 (s, 2H),
2.65 (s, 2H), 1.66 (t, 2H, J = 6.6  14.4 Hz), 1.28 (s, 10H), 0.86 (t, 3H,
J = 5.4  12.0 Hz). 13C NMR (150 MHz, DMSO-d6) d (ppm): 171.85,
160.94, 155.83, 150.02, 147.84, 134.66, 129.89, 129.72, 129.38,
126.13, 123.96, 121.00, 63.51, 34.00, 31.73, 29.29, 29.14, 29.09,
28.83, 24.68, 22.55, 14.40. Elemental analysis calculated (%) for
C28H34BrN3O2: C 64.12, H 6.53, N 8.01; found: C 64.29, H 6.47, N
8.06. FT-IR (KBr, cm
1): 3063, 2921, 2849, 1740, 1633, 1455, 1103,
1077, 868, 698, 570.
(E)-1-(4-Nitrobenzyl)-4-((4-((4-(triuoromethyl)benzoyl)oxy)
phenyl)diazenyl)pyridin-1-ium bromide (Compound 1d): pale
brown solid (0.64 g) yielded 65.2%. Mp: 192.0193.0  C. MS
(ESI): (MeOH, positive mode) m/z: 507.3 (mass = 507.26 g mol
1).

Scheme 3. Synthetic route for compounds 2ac.

150

C.- Gong et al. / Synthetic Metals 220 (2016) 147154

H NMR (600 MHz, DMSO-d6) d (ppm): 9.46 (d, 2H, J = 7.2 Hz), 8.50
(d, 2H, J = 6.6 Hz), 8.38 (d, 2H, J = 7.8 Hz), 8.32 (d, 2H, J = 9.0 Hz), 8.22
(m, 2H, J = 1.8  9.0 Hz), 8.04 (d, 2H, J = 8.4 Hz), 7.84 (d, 2H,
J = 9.0 Hz), 7.73 (m, 2H, J = 1.8  9.0 Hz). 6.14 (s, 2H). 13C NMR
(150 MHz, DMSO-d6): d (ppm): 172.46, 165.23, 149.44, 146.38,
144.92, 140.53, 136.24, 133.51, 130.61, 129.97, 129.24, 125.54,
125.06, 124.17, 123.85, 121.64, 61.98. Elemental analysis calculated
(%) for C26H20BrF3N4O4: C 53.06, H 3.40, N 9.52; found: C 52.89, H
3.53, N 9.60. FT-IR (KBr, cm
1): 3098, 2922, 2851, 1636, 1544, 1453,
1295, 1164, 1076, 820, 729, 560.
2.3. General synthesis of 4,40 -Azobisbenzylpyridine (compounds 2ac)
The synthetic route for compounds 2a-c is depicted in Scheme 3.
4,40 -Azobispyridine was synthesized according to the method
reported by Verma et al. [66]. Orange solid (2.1 g) yielded 77.2%. 1H
NMR (600 MHz, DMSO-d6) d (ppm): 8.90 (d, 4H, J = 5.4 Hz), 7.81 (d,
4H, J = 5.4 Hz).
A typical procedure for the synthesis of compound 2a is
described as follows. In a dry 50 mL ask, 4,40 -azobispyridine
(5.0 mmol) dissolved in acetonitrile (20 mL) and benzyl bromide
(13.0 mmol) were charged, and then heated to reux for 24 h. Thinlayer chromatography (petroleum ether/ethyl acetate = 2:1, v/v)
was performed to monitor the reaction. The mixture was cooled
down to room temperature and ltered. The crude product was
further puried by washing with diethyl ether followed by
recrystallisation from methanol. 4,40 -Azobisbenzylpyridine
bromide (Compound 2a): dark yellow solid (1.43 g) yielded
74.2%. Mp: 246.0247.5  C. MS (ESI): (MeOH, positive mode)
m/z: 183.2 (mass = 366.24 g mol
1, charge = +2). 1H NMR (600 MHz,
DMSO-d6) d (ppm): 9.57 (s, 4H), 8.55 (d, 4H, J = 38.4 Hz), 7.62 (d, 4H,
J = 6.6 Hz), 7.48 (m, 4H, J = 6.6  24.0 Hz), 7.43 (m, 2H, J = 6.0  20.4
Hz), 6.03 (s, 4H). 13C NMR (150 MHz, DMSO-d6): d (ppm): 148.47,
134.48, 130.00, 129.75, 129.53, 128.78, 121.58, 63.98. Elemental
analysis calculated (%) for C24H22BrN4: C 54.77, H 4.21, N 10.65;
found: C 54.90, H 4.15, N 10.69. FT-IR (KBr, cm
1): 3378, 3105, 3080,
3034, 1980, 2933, 1633, 1580, 1456, 791, 739, 611, 557.
In a dry 100 mL ask, KPF6 (3.60 g, 19.6 mmol) dissolved in
methanol (20 mL) was introduced and heated to reux,
compound 2a (1.0 g, 1.9 mmol) in methanol was then added
dropwise and then heated to reux for 1 h. Purple solid was
obtained after cooled to room temperature, ltration, and washed
with water. 4,40 -Azobisbenzylpyridine hexauorophosphate
(Compound 2b): purple solid (0.90 g) yielded 45.6%.

Mp: 215.0215.5  C. MS (ESI): (MeOH, positive mode) m/z:

183.2 (mass = 366.24 g mol
1, charge = +2). 1H NMR (600 MHz,
DMSO-d6) d (ppm): 9.50 (s, 4H), 8.53 (s, 4H), 7.59 (d, 4H), 7.48 (m,
4H, J = 1.8  20.4 Hz), 7.45 (m, 2H, J = 2.4  9.6 Hz), 5.98 (s, 4H). 13C
NMR (150 MHz, DMSO-d6): d (ppm): 160.02, 148.47, 134.44,
130.03, 129.78, 129.43, 121.61, 64.18, 49.07. Elemental analysis
calculated (%) for C24H22F12N4P2: C 43.92, H 3.38, N 8.54; found: C
43.82, H 3.49, N 8.71. FT-IR (KBr, cm
1): 3429, 3132, 3074, 1974,
1634, 1585, 1460, 836 (broad), 727, 697, 558.
In a dry 100 mL ask, LiClO4 (0.45 g, 4.2 mmol) dissolved in
methanol (20 mL) was added and heated to reux, compound 2a
(0.7 g, 1.33 mmol) in methanol was then added dropwise and
subsequently heated to reux for 5 h. Orange solid was obtained
after cooled to room temperature, ltration, and washed with
ethanol and water. 4,40 -Azobisbenzylpyridine perchlorate (Compound 2c): orange solid (0.94 g) yielded 48.2%. Mp: 236.0236.5  C.
MS (ESI): (MeOH, positive mode) m/z: 183.2 (mass = 366.24 g
mol
1, charge = +2). 1H NMR (600 MHz, DMSO-d6) d (ppm): 9.49 (s,
4H), 8.53 (s, 4H), 7.58 (d, 4H, J = 7.2 Hz), 7.50 (m, 4H, J = 6.6  16.8
Hz), 7.42 (d, 2H, J = 7.2 Hz), 5.98 (s, 4H). 13C NMR (150 MHz, DMSOd6): d (ppm): 148.45, 130.04, 129.78, 129.44, 121.58. Elemental
analysis calculated (%) for C24H22F12Cl2N4O8: C 50.99, H 3.92, N
9.91; found: C 51.12, H 3.81, N 9.84. FT-IR (KBr, cm
1): 3421, 3124,
3063, 2834, 1634, 1455, 1075, 1044 (broad), 867, 724, 622, 549.
2.4. ECD construction
ECDs based on compounds 1ad embedded into a sandwich
matrix were constructed according to the method reported by
Gong et al. [60,61] and Fu et al. [67]. Glass coated with indium tin
oxide (conductive side inward) and a reective metallic surface
were placed a fraction of a millimeter apart (35 mm  40 mm
 0.7 mm, 50 V/sq) from each other and used as the two electrodes
of the cell. The electrolyte solution was prepared by dissolving
compounds 1ad (200 mmol), ferrocene (Fc, 100 mmol, as counter
electrode materials), and tetrabutylammonium perchlorate (TBAP,
200 mmol) in dimethyl formamide (DMF, 10.0 mL). Then, the
prepared electrolyte was injected into the developed ECD using a
syringe.
ECDs based on compounds 2ac were constructed using the
same procedure, but utilising an alternative electrolyte solution.
The electrolyte solution was prepared by dissolving compounds
2ac (800 mmol), Fc (800 mmol), and TBAP (120 mmol) in DMF
(10.0 mL).

Fig. 1. Cyclic voltammograms of compounds (A) 1b in DMF/TBAP (0.05 mol L
1) and (B) 2a in propylene carbonate vs. Ag/AgCl at room temperature.

C.- Gong et al. / Synthetic Metals 220 (2016) 147154

151

Azobenzene-bridged neutralcationic materials (compounds

1ad) showed less reversible and stable properties.

3. Results and discussion

3.1. Electrochemical properties

3.2. Spectroelectrochemical properties

Electrochemical measurements were performed via CV (cyclic
voltammetry) at room temperature in a conventional threeelectrode system [68]. The working and counter electrodes were a
platinum disk (0.02 cm2) and a platinum wire, respectively.
Ag/AgCl was used as the reference electrode. Compounds 1ad
exhibited quasi-reversible one-electron reduction. Using compound 1b (Fig. 1A) as an example, a redox couple was observed at
ca.
0.233 V and
0.338 V. The redox couples of compounds 1a, 1c,
and 1d were observed at ca.
0.224 V and
0.339 V,
0.252 V and

0.366 V, and
0.226 V and
0.329 V, respectively. This result
illustrated that the substituents did not signicantly inuence the
electrochemical process. The cyclic voltammograms of compounds
2ac presented results similar to those of double carbon bondbridged pyridinium salts [69]. Using compound 2a (Fig. 1B) as an
example, two main couples of redox waves were observed at ca.
0.340 V and 0.419 V and at ca. 0.033 V and 0.123 V, which could be
attributed to the reduction of bleached dicationic pyridinium salts
into monovalent radical cation an then into neutral azopyridinium
(Scheme 4) [63,64]. The rst reduction peak at ca. 0.340 V, with
scans in the negative direction, was attributed to the reduction of
the bleached dicationic pyridinium salts into colored monovalent
radical cation. The second reduction peak at ca. 0.033 V corresponded to further reduction that led to the formation of a neutral
state. Similar results were obtained for compounds 2b and 2c, i.e.,
the reduction peaks were at ca. 0.333 V and 0.033 V for compound
2b and at ca. 0. 336 V and 0.031 V for compound 2c. This nding
demonstrated that anions (Br
, PF6
, and ClO4
) did not inuence
the electrochemical properties of azopyridinium. Azobenzenebridged neutralneutral materials exhibited two pairs of separated
redox peaks [60]. Azobenzene-bridged cationiccationic (compounds 2ac) and neutralneutral showed excellent electrochemical reversibility and stability after more than 100 cycles. However,

Fig. 2 shows the UVvis spectroelectrochemistry and photographs of compounds 1b and 2a in colored and bleached states. As
shown in Fig. 2A for compound 1b in bleached state, a weak and
broad absorption peak with an orangered color appeared at
around 480 nm. Under the applied potential of 1.8 V, a strong
absorption peak appeared at around 455 nm, and the color
changed from orangered to brown. For compound 2a (Fig. 2B),
a new absorption peak appeared at ca. 460 nm upon the
application of 1.7 V, and the color changed from light yellow in
the bleached state to red in the colored state. For azobenzenebridged neutralneutral materials, a broad and weak absorption
band centered at 446 nm was observed in the bleached state. After
the applied voltage was increased to 3.0 V, the previous absorption
band was red-shifted to 508 nm, its intensity increased signicantly, and color changed from colorless to magenta [60].
Azobenzene-bridged neutralneutral, cationicneutral, and
cationiccationic materials exhibited a distinct change in color
between bleached and colored states.
3.3. Electrochromic switching studies
ECDs based on compounds 1ad and 2ac were switched under
ambient conditions via repeated potential steps between oxidized
and reduced states with a residence time of 4 s at around 455, 460,
and 508 nm, respectively. Absorbances were monitored at lmax.
Meanwhile, the ECDs were switched between 0.0 V and 1.8 V for
compound 1b and 0.0 V and 1.7 V for compound 2a, respectively.
Optical contrast (DT%) is a common measure of the intensity of
coloration for ECMs between the bleached and colored states. As
shown in Fig. 3, the maximum DT% of compounds 1b and 2a were
35% at 455 nm and 40% at 460 nm respectively. The maximum DT%

Scheme 4. Structures of compounds 1ad and 2ac during electrochemical reduction.

152

C.- Gong et al. / Synthetic Metals 220 (2016) 147154

Fig. 2. UVvis spectroelectrochemistry and photographs of compounds (A) 1b and (B) 2a in bleached and colored states.

Fig. 3. Electrochromic switching responses monitored at (A) 455 nm for compound 1b and (B) 460 nm for compound 2a between
1.8 V and 1.8 V with a residence time of 4 s.

of compounds 1a, 1c, 1d, 2b, and 2c were 40%, 42%, 35%, 50%, and
40%, respectively.
Response time, one of the most important characteristics of
ECMs, is the time required to perform switching between the two
colored states of a materials. Switching time was quantied by
dening a change in 95% of the total absorbance span, because the
naked eye could not distinguish color change after this point [70].
As shown in Fig. 4, the time required to attain 95% of the total
transmittance difference for the reduction and oxidation processes
was 1.95 s and 0.98 s for compound 1a, 1.93 s and 0.97 s for

compound 1b, 1.94 s and 0.96 s for compound 1c, 1.93 s and 0.94 s
for compound 1d, 1.93 s and 1.89 s for compound 2a, 1.92 s and
1.91 s for compound 2b, and 1.93 s and 1.91 s for compound 2c. The
two groups of compounds presented rapid switching time within
the range of a few seconds, and the colored time was slower than
the bleached time, which may be attributed to the interface block
during ion injection and transport [69]. The response time of the
compounds with pyridinium salts was slower than those with
esters [60,61]. This nding was attributed to the reduction
properties of the pyridinium unit [63]. The substituents of

Fig. 4. Results of the optical switching studies of ECDs based on compounds (A) 1b and (B) 2a monitored at 455 and 460 nm, respectively.

C.- Gong et al. / Synthetic Metals 220 (2016) 147154

compounds 1ad and the anions of compounds 2ac did not

signicantly inuence response time.
Coloration efciency (CE) is an important characteristic for
ECMs when comparing among ECMs and ECDs [71]. CE value can be
calculated by Eqs. (1) and (2) [72]:
T
Tc

DOD log b

153

Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (20872121), Chong Qing Science and
Technology Commission (2013jcyjA50026), Chongqing City Board
of Education (CY150206), and the Southwest University Doctoral
Fund (SWUB2008075).
Appendix A. Supplementary data

CEh

DOD

Qd

where Tc and Tb are the light transmittances of the colored state

and the bleached state, respectively, of an ECD at a certain
wavelength (l). DOD denotes the change in optical density, which
is proportional to the amount of created color centers. h denotes
CE, and Qd indicates the amount of injected/ejected charge per unit
sample area. On the basis of these equations, DOD and CE were
calculated to be 0.97 and 1043 cm2/C for compound 1a at 454 nm,
0.99 and 1065 cm2/C for compound 1b at 455 nm, 0.86 and
925 cm2/C for compound 1c at 453 nm, 0.80 and 860 cm2/C for
compound 1d at 441 nm, 0.32 and 344 cm2/C for compound 2a at
458 nm, 0.76 and 817 cm2/C for compound 2b at 460 nm, and 0.75
and 807 cm2/C for compound 2c at 459 nm. From the CE data in
Table 1, azobenzene-bridged cationicneutral (compounds 1a1d)
and neutralneutral materials (compounds 3a3f) clearly exhibited higher CE than c azobenzene-bridged cationiccationic
(compounds 2a2c). The possible reason for this result is that
the radicals formed during the reduction of compounds 2ac are
unstable.
4. Conclusions
Azobenzene-bridged neutralcationic and cationiccationic
ECMs were synthesised, and their electrochemical and electrochromic properties were investigated and compared with
azobenzene-bridged neutralneutral materials. Among these
compounds, azobenzene-bridged cationiccationic and neutral
neutral materials exhibited well-dened and reversible redox
couples during redox processes. Azobenzene-bridged neutral
neutral ECMs demonstrated fast response time, higher DOD and
CE, and the maximum DT%. Azobenzene-bridged neutral-cationic
material displayed less reversible and stable properties.

Table 1
Optical and electrochromical data of azobenzene-bridged cationicneutral
(compounds 1a1d), cationiccationic (2a2c), and neutralneutral (3a3f)
materials.\
Compounds

Response time (s)

DOD

CE (cm2/C)

DT%

Reference

Colored

Bleached

1a
1b
1c
1d

1.95
1.93
1.94
1.93

0.98
0.97
0.96
0.94

0.97
0.99
0.86
0.80

1043
1065
925
860

40%
35%
42%
35%

This
This
This
This

2a
2b
2c

1.93
1.92
1.93

1.89
1.91
1.91

0.32
0.76
0.75

344
817
807

40%
50%
40%

This work
This work
This work

3a
3b
3c
3d
3e
3f

1.36
0.96
1.21
0.93
1.24
0.92

0.90
0.89
1.12
0.83
1.02
0.86

0.16
0.99
1.08
0.92
0.15
0.93

171
1074
1161
989
172
1100

15%
66%
65%
62%
21%
67%

[60]
[60]
[60]
[60]
[60]
[60]

work
work
work
work

Supplementary data associated with this article can

be found, in the online version, at http://dx.doi.org/10.1016/j.
synthmet.2016.06.011.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

[10]
[11]
[12]

[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]

G.A. Niklasson, C.G. Granqvist, J. Mater. Chem. 17 (2007) 127.

J. Jensen, M. Hosel, A.L. Dyer, F.C. Krebs, Adv. Funct. Mater. 25 (2015) 2073.
R.D. Rauh, Electrochim. Acta 44 (1999) 3165.
Y. Kim, J. Do, E. Kim, G. Clavier, L. Galmiche, P. Audebert, J. Electroanal. Chem.
632 (2009) 201.
A. Piccolo, A. Pennisi, F. Simone, Sol. Energy 83 (2009) 832.
S.M. Wang, L. Liu, W.L. Chen, E.B. Wang, Electrochim. Acta 113 (2013) 240.
P.M.S. Monk, J. Electroanal. Chem. 432 (1997) 175.
K. Bange, Sol. Energ. Mat. Sol. C 58 (1999) 1.
A.T. Peters, H.S. Freeman, Color Chemistry: The Design and Synthesis of
Organic Dyes and Pigments, Appl Sci Publ Ltd, Barking, Essex, 1991, pp.
193195.
D.S.K. Mudigonda, D.L. Meeker, D.C. Loveday, J.M. Osborn, J.P. Ferraris, Polymer
40 (1999) 3407.
I.D. Brotherson, D.S.K. Mudigonda, J.M. Ocborn, J. Belk, J. Chen, D.C. Loveday, J.L.
Boehme, J.P. Ferraris, D.L. Meeker, Electrochim. Acta 44 (1999) 2993.
A.A. Argun, P.H. Aubert, B.C. Thompson, I. Schwendeman, C.L. Gaupp, J. Hwang,
N.J. Pinto, D.B. Tanner, A.G. MacDiarmid, J.R. Reynolds, Chem. Mater. 16 (2004)
4401.
G. Sonmez, Chem. Commun. 42 (2005) 5251.
J.R. Platt, J. Chem. Phys. 34 (1961) 862.
Z.J. Yao, J.T. Di, Z.Z. Yong, Z.G. Zhao, Q.W. Li, Chem. Commun. 48 (2012) 8252.
S.K. Deb, Philos. Mag. 27 (1973) 801.
X.T. Chang, S.B. Sun, L.H. Dong, X. Hu, Y.S. Yin, Electrochim. Acta 129 (2014) 40.
Y.X. Wei, J.L. Zhou, J.M. Zheng, C.Y. Xu, Electrochim. Acta 166 (2015) 277.
Y.P. Tian, M.L. Zhang, X.Q. Yu, G.B. Xu, Y. Ren, S.Y. Zhang, M.H. Jiang, Chem. Phys.
Lett. 338 (2004) 325.
S.K. Kim, C.J. Lee, I.N. Kang, J.H. Lee, J.W. Park, Thin Solid Films 509 (2006) 132.
X.P. Qiu, R. Lu, H.P. Zhou, X.F. Zhang, T.H. Xu, X.L. Liu, Y.Y. Zhao, Tetrahedron
Lett. 48 (2007) 7582.
J. Simokaitiene, J.V. Grazulevicius, V. Jankauskas, R. Rutkaite, J. Sidaravicius,
Dyes Pigm. 79 (2008) 40.
J.H. Huang, K.C. Li, H.Y. Wei, P.Y. Chen, L.Y. Lin, D. Kekuda, H.C. Lin, K.C. Ho, C.W.
Chu, Org. Electron. 10 (2009) 1109.
D.H. Choi, K.I. Han, I.H. Chang, S.H. Choi, X.H. Zhang, K.H. Ahn, Y.K. Lee, J. Jang,
Synth. Met. 157 (2007) 332.
B.L. Sui, X.K. Fu, Dyes Pigm. 83 (2009) 1.
B.L. Sui, X.K. Fu, J. Solid State Electr. 13 (2009) 1889.
W.A. Badawy, K.M. Ismail, S.S. Medany, Electrochim. Acta 51 (2006) 6353.
G. Wang, X.K. Fu, J. Huang, L. Wu, Q.L. Du, Electrochim. Acta 55 (2010) 6933.
J. Zheng, Y.J. Zheng, X.H. Wan, Z.Y. Wang, Chin. J. Polym. Sci. 30 (2012) 328.
F.K. Chen, J. Zhang, H. Jiang, X.H. Wan, Chem-Asian J. 8 (2013) 1497.
B. Yao, X.C. Ye, J. Zhang, X.H. Wan, Org. Lett. 16 (2014) 5378.
W.Q. Qiao, J. Zheng, Y.F. Wang, Y.J. Zheng, N.H. Song, X.H. Wan, Z.Y. Wang, Org.
Lett. 10 (2008) 641.
R. Sydam, M. Deepa, A.G. Joshi, Org. Electron. 14 (2013) 1027.
P.Y. Chen, C.S. Chen, T.H. Yeh, J. Appl. Ploym. Sci. 131 (2014) 40485.
M. Li, Y.X. Wei, J.M. Zheng, D. Zhu, C.Y. Xu, Org. Electron. 15 (2014) 428.
T.M. Benedetti, T. Carvalho, D.C. Lwakura, F. Braga, B.R. Vieira, P. Vidinha, J.
Gruber, R.M. Torresi, Sol. Energ Mat. Sol. C 132 (2015) 101.
S. Okada, K. Yamada, J. Mol. Struct. 1037 (2013) 256.
D.Z. Mo, S.J. Zhen, J.K. Xu, W.Q. Zhou, B.Y. Lu, G. Zhang, Z.P. Wang, S.M. Zhang, Z.
L. Feng, Synthetic Met. 198 (2014) 19.
A. Capan, T. Ozturk, Synthetic Met. 188 (2014) 100.
X.T. Wu, W. Wang, B. Li, Y.J. Hou, H.J. Niu, Y.H. Zhang, S.H. Wang, X.D. Bai,
Spectrochim. Acta A 140 (2015) 398.
J. Roncali, Chem. Rev. 92 (1992) 711.
A.L. Dyer, C.R.G. Grenier, J.R. Reynolds, Adv. Funct. Mater. 17 (2007) 1480.
P. Andersson, R. Forchheimer, P. Tehrani, M. Berggren, Adv. Funct. Mater. 17
(2007) 3074.
B.D. Reeves, E. Unur, N. Ananthakrishnan, J.R. Reynolds, Macromolecules 40
(2007) 5344.
A. Durmus, G.E. Gunbas, L. Toppare, Chem. Mater. 19 (2007) 6247.
C.G. Wu, M.I. Lu, S.J. Chang, C.S. Wei, Adv. Funct. Mater. 17 (2007) 1063.

154

C.- Gong et al. / Synthetic Metals 220 (2016) 147154

[47] S. Cogal, M. Kiristi, K. Ocakoglu, L. Oksuz, A.U. Oksuz, Mat. Sci. Semicon. Proc.
31 (2015) 551.
[48] F. Rourke, J.A. Crayston, J. Chem. Soc. Faraday Trans. 89 (1993) 295.
[49] D. Djurado, B. Gilles, P. Rannou, J.P. Travers, Synthetic Met. 101 (1999) 803.
[50] S.X. Xiong, Z.F. Li, M. Gong, X.Q. Wang, J.L. Fu, Y.J. Shi, B.J. Wu, J. Chu,
Electrochim. Acta 138 (2014) 101.
[51] D. Delongchamp, P.T. Hammond, Adv. Mater. 13 (2001) 1455.
[52] T.S. Tung, K.C. Ho, Sol. Energ Mat. Sol. C 90 (2006) 521.
[53] K. Honda, J. Ochiai, H. Hayashi, J. Chem. Soc. Chem. Commun. 2 (1986) 168.
[54] S.X. Xiong, F. Yang, G.Q. Ding, K.Y. Mya, J. Ma, X.H. Lu, Electrochim. Acta 67
(2012) 194.
[55] L.N. Ma, H.J. Niu, J.W. Cai, P. Zhao, C. Wang, X.D. Bai, Y.F. Lian, W. Wang, Carbon
67 (2014) 488.
[56] L. He, H.S. Freeman, M. Nakpathom, P.D. Boyle, Dyes Pigm. 120 (2015) 245.
[57] Y.B. Wei, Q. Tang, C.B. Gong, M.H.W. Lam, Anal. Chim. Acta 900 (2015) 10.
[58] K. Imaizumi, Y. Watanabe, K. Nakamura, T. Omatsu, N. Kobayashi, Phys. Chem.
Chem. Phys. 13 (2011) 11838.
[59] N. Kobayashi, S. Miura, M. Nishimura, H. Urano, Sol. Energ Mat. Sol. C 92 (2008)
136.

[60] L.H. He, G.M. Wang, Q. Tang, X.K. Fu, C.B. Gong, J. Mater. Chem. C 2 (2014) 8162.
[61] Q. Tang, L.H. He, Y.H. Yang, J.F. Long, X.K. Fu, C.B. Gong, Org. Electron. 30 (2016)
200.
[62] W. Sharmoukh, K.C. Ko, J.H. Ko, H.J. Nam, D.Y. Jung, C. Noh, J.Y. Lee, S.U. Son, J.
Mater. Chem. 18 (2008) 4408.
[63] G.M. Wang, X.K. Fu, L.H. He, X.M. Huang, Q. Miao, Org. Electron. 15 (2014) 622.
[64] R. Sydam, A. Ghosh, M. Deepa, Org. Electron. 17 (2015) 33.
[65] H.D. Lu, J.X. Wang, X.Z. Song, Mol. Cryst. Liq. Cryst. 537 (2011) 93.
[66] S. Verma, V. Vajpayee, S.M. Lee, H.J. Jung, H. Kim, K.W. Chi, Inorg. Chim. Acta
387 (2012) 435.
[67] G.M. Wang, X.K. Fu, J. Deng, X.M. Huang, Q. Miao, Chem. Phys. Lett. 579 (2013)
105.
[68] I. Kaya, M. Yildirim, A. Aydin, Org. Electron. 12 (2011) 210.
[69] J. Deng, X.K. Fu, G. Wang, L. Wu, J. Huang, Electrochim. Acta 85 (2012) 195.
[70] Q. Du, Y.X. Wei, J.M. Zheng, C.Y. Xu, Electrochim. Acta 132 (2014) 258.
[71] C.B. Ran, H.L. Peng, L. Ren, W. Zhou, Y.D. Ling, Z.F. Liu, J. Phys. Chem. C 111
(2007) 631.
[72] B. Yigitsoy, S. Varis, C. Tanyeli, I.M. Akhmedov, L. Toppare, Electrochim. Acta 52
(2007) 6561.