J Solid State Electrochem (2009) 13:1889–1895

DOI 10.1007/s10008-008-0767-0

ORIGINAL PAPER

Novel application of 1-/2-phenyl substituted 9,

10-anthraquinones in solid electrochromic devices
Binglin Sui & Xiangkai Fu

Received: 19 November 2008 / Revised: 2 December 2008 / Accepted: 3 December 2008 / Published online: 16 December 2008
# Springer-Verlag 2008

Abstract 1-/2-phenyl substituted 9,10-anthraquinones the materials, organic chromophores have merits suitable for
were synthesized via Suzuki coupling reactions of 1-/2- these displays because of their low-driving voltage, high
iodo-9,10-anthraquinones with benzeneboronic acid. They contrast, flexible switching, color-mixing capability, and
are efficient and reversible electrochromic materials and simple device setup [13].
their solid electrochromic devices were prepared. When Various types of electrochromic materials have been
reduced, the device color of 1-phenyl-9,10-anthraquinone developed, including transition-metal complexes [14–16],
shifts from yellow to claret while that of 2-phenyl-9,10- conjugated polymers [17–20], viologens [21–24], aromatic
anthraquinone switches from yellow-green to a dark blue- diquinones [25–26], and aromatic imides [27–30]. Anthra-
purple. Their different characteristics and behaviors in quinone derivatives are efficient and interesting electro-
electrochromic devices are only determined by the different chromic materials but haven’t received much attention
substituted positions of the phenyl group. They are except a few reports about polyanthraquinones and anthra-
potentially to be widely applied in commercial application quinone imides [31–35]. Herein, we report a more efficient
for the excellent behaviors plus the inexpensive starting synthesis of 1-/2-phenyl-9,10-anthraquinones (PAQs)
materials and short synthetic routes. through the diazotization–Sandmeyer and Suzuki coupling
reactions and discuss their different characteristics and
Keywords Phenylanthraquinones . Electrochromism . behaviors in cyclic voltammograms (CV) and electro-
Electrochromic materials . Solid electrochromic devices . chromic devices. They are redox active because the
Resonance structures phenyl-substituted group extends the degree of conjugation
of anthraquinone. So, they are efficient and reversible
electrochromic materials. When reduced, the device color
Introduction of 1-phenyl-9,10-anthraquinone shifts from yellow to claret
while that of 2-phenyl-9,10-anthraquinone switches from
Electrochromic (EC) materials are currently attracting much yellow-green to dark blue-purple.
interest in academia and industry for both their fascinating
spectroelectrochemical properties and their commercial appli-
cations [1–5]. A great deal of research regarding these Experimental
materials has focused on the applications of light-modulating
devices, such as smart windows, variable reflectance mirrors, General Data All manipulations involving air-sensitive
and information display and storage devices [6–12]. Among reagents were performed in an atmosphere of dry argon.
All chemicals and reagents, unless otherwise specified,
B. Sui : X. Fu (*) were purchased from Aldrich, Acros, and TCI Chemical
Research Institute of Applied Chemistry, and used as received. All the solvents were further purified
School of Chemistry and Chemical Engineering,
before use. All new compounds were characterized by 1H
Southwest University,
Chongqing 400715, People’s Republic of China NMR, 13C NMR, MS, and IR. 1H NMR spectra were
e-mail: [email protected] measured on a Bruker AV300 (300 MHz) spectrometer at
1890 J Solid State Electrochem (2009) 13:1889–1895

added in portions with stirring to concentrated sulfuric acid

(5 mL). To this solution, maintained at a temperature of 10 to
15 °C, was added dropwise the solution of sodium nitrite
(0.15 g, 2.2 mmol) in concentrated sulfuric acid (1 mL)
under argon. The diazonium salt solution resulted was stirred
Fig. 1 Structure of the transparent solid EC devices. 1 glass, 2 ITO, 3 for further 2 h and then poured into adequate amount of ice.
insulating epoxy resin, 4 gel electrolyte, 5 PAQs films The precipitate formed was passed through a glass filter and
dissolved in water (25 mL) at room temperature while still
wet and the solution was filtered from the impurities to yield
the ambient temperature with CDCl3 as the solvent and a brownish filtrate. A solution of potassium iodide (0.4 g,
tetramethylsilane as an internal standard. 13C NMR spectra 24.0 mmol) in water (1 mL) was then dropwise added. After
were recorded on Bruker AV300 (75 MHz) spectrometer at the resulting reaction mixture was stirred at room tempera-
the ambient temperature with CDCl3 as the solvent. Chemical ture for 5 h, a solution of Na2S2O3 was added to remove I2.
shifts were recorded in ppm from the solvent resonance The crude product was collected by filtration and purified by
employed as the internal standard (CDCl3 at 77 ppm). silica gel column chromatography, eluting with hexane/
Melting points were determined by differential scanning methylene chlorideB=1/1.
calorimetry (TA Q100) at a heating rate of 10 °C/min under
Ar atmosphere. Atmospheric pressure chemical ionization 1-Iodoanthraquinone (1) Yield: 87% M.p.: 204–205 °C;
mass spectra (APCI-MS) were obtained on a Bruker HCT δH (300 MHz, CDCl3): 8.24–8.44 (m, 4 H), 7.80 (s, 2 H),
mass spectrometer. Infrared spectroscopic measurements 7.39 (t, 3JHH =7.5 Hz, 1 H); δC (75 MHz, CDCl3):
were performed in the range of 4,000–400 cm−1 on a Bruker 181.8 (C=O), 181.4 (C=O), 148.6, 135.8, 134.5, 134.0,
Tensor 27 FT-IR spectrometer. Cyclic voltammetry was 133.8, 132.6, 132.2, 128.3, 127.7, 126.7, 93.2; FT-IR (KBr,
carried out on a CHI 650B electrochemical workstation at a cm−1): 1,676 (s), 1,590 (m), 1,566 (m), 1,314 (s), 1,264 (s),
scan rate of 100 mV/s with platinum wire and saturated 1,156 (m), 1,104 (m), 948 (m), 806 (m), 702 (s); MS (m/z):
calomel electrodes (SCE) as the counter and reference 334.1 (M+).
electrodes, respectively. The solutions were made in CH2Cl2
containing 0.1 M tetra-n-butylammonium perchlorate 2-Iodoanthraquinone (3) Yield: 85% M.p.: 172–173 °C;
(TBAP) and were degassed with argon prior to electro- δH (300 MHz, CDCl3): 8.59 (s, 1 H), 8.25 (s, 2 H), 8.11 (d,
3
chemical work. Spectroelectrochemical data were performed JHH =7.9Hz, 1 H), 7.96 (d, 3JHH =7.9 Hz, 1 H), 7.80 (s,
on a Unico UV-4802H UV-visible spectrophotometer con- 2 H); δC (75 MHz, CDCl3): 182.5 (C=O), 181.8 (C=O),
nected to a computer in an optical transparent thin layer cell. 143.0, 136.2, 134.4, 134.3, 133.9, 133.2, 132.9, 132.4,
128.6, 127.3, 127.2, 102.2; FT-IR (KBr, cm−1): 3,062 (w),
General procedure for the synthesis of iodoanthraquinones 1,674 (s), 1,568 (s), 1,321 (s), 1,289 (s), 1,163 (m),
A sample of aminoanthraquinone (0.45 g, 2.0 mmol) was 925 (m), 897 (m), 849 (m), 707 (s); MS (m/z): 334.1 (M+).

O O O
B(OH)2
1) H2SO4, NaNO2

2) KI Pd(PPh3)4
K2CO3
O NH2 O I O Ph
[CH3(CH2)3]4NBr
1 90oC 2
Toluene/H2O

O O O
B(OH)2
1) H2SO4, NaNO2

2) KI Pd(PPh3)4
NH2 I Ph
O K2CO3
O O
[CH3(CH2)3]4NBr
3 90oC 4
Toluene/H2O

Scheme 1 Synthetic route of target molecules

J Solid State Electrochem (2009) 13:1889–1895 1891

The organic layer was dried over MgSO4 and evaporated.

The crude product was collected by filtration and purified by
silica gel column chromatography, eluting with hexane/
methylene chloride=1/1.

1-Phenylanthraquinone (2) Yield: 98% M.p.: 178–179 °C;

δH (300 MHz, CDCl3): 8.37 (d, 3JHH =7.2 Hz, 1 H), 8.25 (s,
1 H), 8.10 (s, 1 H), 7.73 (s, 3 H), 7.59 (d, 3JHH =6.9 Hz,
1 H), 7.44 (s, 3 H), 7.30 (s, 2 H); δC (75 MHz, CDCl3):
183.3 (C=O), 183.2 (C=O), 144.3, 141.9, 137.7, 134.7,
134.5, 134.2, 133.6, 132.8, 132.7, 130.8, 128.0, 127.9, 127.3,
127.2, 126.7; FT-IR (KBr, cm−1): 3,098 (w), 3,061 (w), 1,673
(s), 1,593 (m), 1,577 (m), 1,319 (s), 1,275 (s), 1,159 (m), 949
(m), 789 (m), 760 (m), 707 (s); MS (m/z): 284.3 (M+).
Fig. 2 Cyclic voltammetry of a 2 (5.0×10−3 M) and b 4 (5.0×
10−3 M) in CH2Cl2/TBAP (0.1 M) at room temperature, scan rate of 2-Phenylanthraquinone (4) Yield: 96% M.p.: 158–159 °C;
100 mV/s, Pt disk working electrode (a radius of 4 mm)
δH (300 MHz, CDCl3): 8.50 (s, 1 H), 8.31–8.35 (m, 3 H),
7.80 (d, 3JHH =7.7 Hz, 1 H), 7.78 (s, 2 H), 7.70 (d, 3JHH =
General procedure for the synthesis of phenylanthraquinones 6.8 Hz, 2 H), 7.44–7.50 (m, 3H); δC (75 MHz, CDCl3):
To a stirred mixture of benzeneboronic acid (0.15 g, 183.1 (C=O), 182.8 (C=O), 146.7, 138.8, 134.1, 134.0,
1.2 mmol) and iodoanthraquinone (0.33 g, 1.0 mmol) in 133.8, 133.6, 133.5, 132.3, 132.1, 129.1, 128.8, 128.0,
toluene (3.5 mL) was added a 2 M aqueous potassium 127.3, 127.2, 127.1, 125.5; FT-IR (KBr, cm−1): 3,063 (w),
carbonate solution (2.5 mL) followed by the addition of 3,035 (w), 1,675 (s), 1,593 (s), 1,330 (s), 1,308 (s), 1,161 (w),
phase-transfer agent tetra-n-butylammonium bromide 931 (m), 906 (m), 859 (w), 709 (s); MS (m/z): 284.3 (M+).
(0.32 g, 1.0 mmol). The mixture was bubbled with argon
for 15 min. Then, tetrakis(triphenylphosphine)palladium(0) Preparation of the gel electrolyte The gel electrolyte used
[Pd(PPh3)4] (0.05 g, 0.04 mmol) was added, and the mixture for electrochromic devices was prepared using LiClO4:
was bubbled with argon for an additional 10 min. The ACN:PMMA:PC in the ratio of 3:70:7:20 by weight. After
mixture was vigorously stirred at 90 °C for 24 h under argon. the dissolution of LiClO4 in ACN, poly(methyl methacry-
After the mixture was cooled to room temperature, it was late) (PMMA), (M, 350,000) was added into the solution.
diluted with chloroform and washed with water (3×5 mL). Vigorous stirring and heating was applied to dissolve

Fig. 3 UV-vis absorption

spectra of PAQs in CH2Cl2 at
room temperature in neutral
and radical anion states.
a 2 (3.0×10−4 M containing
0.1 M TBAP) in neutral state;
b 4 (1.5×10−4 M containing
0.1 M TBAP) in neutral state;
c 2 (3.0×10−4 M containing
0.1 M TBAP) in radical anion
state; d 4 (1.5×10−4 M
containing 0.1 M TBAP) in
radical anion state
1892 J Solid State Electrochem (2009) 13:1889–1895

heated until the highly conducting transparent gel was

produced [36].

EC devices fabrication The PAQs were dissolved in a

solution of polyvinyl formal (PVF) polymer in THF. Then
the mixture was spread on ITO/glass (10 Ω) by spin-coating
and dried in vacuum desiccator. The gel electrolyte was
spread on ITO/glass (10 Ω) by spin-coating to make the
counter electrode. Electrochromic devices with PAQs on
ITO/glass (10 Ω) and the corresponding counter electrode
were laminated together at elevated temperature and
pressure. The edges of the devices were sealed with an
insulating epoxy resin (Fig. 1). Electrical contacts were
produced by applying an electrically conducting copper
tape onto overlapping ITO/glass areas. The operation area
Fig. 4 Photographs of EC devices in neutral and redox states. a 2 in was about 3.5×1 cm2.
neutral state, b 2 in redox state at a potential of −3.5 V, c 4 in neutral
state, d 4 in redox state at a potential of −3.0 V
Results and discussion
PMMA. Propylene carbonate (PC), as plasticizer, was
introduced to the reaction medium when all of the PMMA The synthetic procedure for all derivatives is outlined in
was completely dissolved. The mixture was stirred and Scheme 1. The synthesis of phenylanthraquinones (2 and 4)
Scheme 2 Resonance structures
and electron delocalization of 2
in radical anion state
J Solid State Electrochem (2009) 13:1889–1895 1893

was accomplished through the Suzuki coupling reaction relative to the internal SCE. No product of the reduction of
between benzeneboronic acid and iodoanthraquinones (1 the PAQs adheres to the electrode surface in the proceeding
and 3). The preparation of intermediates (1 and 3) via the of the whole experiment. For the two PAQs, two reduction
diazotization–Sandmeyer reaction is very important. There waves were revealed, indicating the formation of stable
was a report about the preparation of 1-iodoanthraquinone radical anions and dianions, respectively. 1-PAQ is reduced

that carried out in water and concentrated hydrochloric acid at the higher potential Ered10
¼ 1:39V; Ered2
0
¼ 1:92V
[37]. But it isn’t the most useful method for the synthesis of and 2-PAQ shows the lower potential Ered1 0
¼ 1:21V;
iodoanthraquinones because of the poor solvation of 0
Ered2 ¼ 1:71VÞ. These data are quite different from that of
aminoanthraquinones in concentrated hydrochloric acid. the unsubstituted anthraquinone which has only one redox
The basicity of aminoanthraquinones is too weak owing peak under the same conditions. So, the board CVs are
to two electron-attracting groups (carbonyl) were attached specific to PAQs. The above data suggest that the positions of
to the amido substituted aromatic ring. Thus, the stronger substituted groups can strongly influence the electrochemical
concentrated sulfuric acid was used instead of concentrated properties of anthraquinone derivatives. These results indicate
hydrochloric acid as the solvent to get a solution rather than that the electron structure of anthraquinone derivatives can be
a suspension. Meanwhile, the sodium nitrite was also efficiently tuned by introducing substituted groups at different
dissolved in concentrated sulfuric acid instead of water substituted positions.
before adding into the solution for the poor stability of The spectrochemical properties of the PAQs were
diazonium salt in water. As a result, products with the high determined by UV-vis in dichloromethane. Figure 3a, b
yield were obtained. shows the normalized UV-vis absorptions of 1-PAQ and 2-
The redox properties of the PAQs were investigated by PAQ, respectively. Two distinct absorption bands are
CV in CH2Cl2 and TBAP as an electrolyte in an electro- observed. The strong absorption peaks of 2 at 253 nm
chemical cell (Fig. 2). Reduction potentials were measured while 4 at 245 nm, the shoulder peaks of 2 at 272 nm while

Scheme 3 Resonance structures and electron delocalization of 4 in radical anion state

1894 J Solid State Electrochem (2009) 13:1889–1895

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