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F. Chen et al. / Electrochimica Acta 99 (2013) 211–218
added dropwise. After addition, the solution was allowed to warm
up to room temperature for overnight reaction. After quenching
of the reaction with ammonium chloride solution, the water layer
was extracted with chloroform and the combined organic layer
was dried over MgSO4. After the remove of the solvent under
reduced pressure, the residue was purified by silica gel column
chromatography (petroleum ether/dichloromethane 1:1) to afford
the product as white solids.
structures which are widely used as hole-transporting and pho-
with a noticeable change of coloration [50–53]. Liou et al. have
intensively explored EC materials based on TPA-containing poly-
imides which show interesting multichromism, good reversibility
poration of electron-donating substituents such as methoxyl group
at the para-position of phenyl groups of TPA unit could not only
stabilize the TPA cationic radicals but also decrease the oxidation
potential [58,59]. In the meanwhile, additional interesting proper-
ties could be expected by combining the different electron-rich and
electron-deficient groups in one single molecule.
In this work, herein, we reported the synthesis and characteri-
zation of three star-shaped donor (D)-acceptor (A) molecules with
different electron-deficient AQI arms connected to the electron-
rich TPA core. The ambipolar character of these molecules was
revealed by electrochemical and spectroelectrochemical studies
and single layer EC device was fabricated. Upon oxidation to radi-
cal cations or reduction to radical anions, intense NIR absorptions
were observed. Multicolor could also be achieved in one single
material at different redox states, e.g., for TPA-AQI, Indian-red at
the neutral state, bluish green at the radical cationic state, olive
green at the radical anionic state, and dark blue at the dianion
state. Furthermore, detailed electronic transitions of the neutral
and radical absorptions were investigated by theoretical calcula-
tions.
2.2.2. 4-Methoxy-N-(4-methoxyphenyl)-N-[4-(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]benzenamine (2a)
Following general procedure A, 1a (1.67 g, 4.3 mmol), n-
BuLi (3 mL, 6.6 mmol) and 2-isopropoxy-4,4,5,5-tetramethyl-
[1,3,2]dioxaborolane (1.09 g, 5.9 mmol) were stirred in dry THF
(20 mL) overnight. Silica gel column chromatography afforded 2a
as white solids (0.62 g, 33%). 1H NMR (300 MHz, CDCl3): ı = 7.60 (br,
2H), 7.06 (br, 4H), 6.84 (d, J = 8.4 Hz, 6H), 3.80 (s, 6H), 1.32 ppm (s,
12H).
2.2.3. N-(4-methoxyphenyl)-4-(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)-N-[4-(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)phenyl]benzenamine (2b)
Following general procedure A, 1b (2.17 g, 5.0 mmol), n-
BuLi (6 mL, 13.2 mmol) and 2-isopropoxy-4,4,5,5-tetramethyl-
[1,3,2]dioxaborolane (2.28 g, 12.2 mmol) were stirred in dry THF
(50 mL) overnight. Silica gel column chromatography afforded 2b
as white solids (1.60 g, 61%). 1H NMR (300 MHz, CDCl3); ı = 7.66 (d,
J = 8.1 Hz, 4H), 7.08 (d, J = 8.7 Hz, 2H), 7.03 (d, J = 8.4 Hz, 4H), 6.86 (d,
J = 8.7 Hz, 2H), 3.81 (s, 3H), 1.33 ppm (s, 24H).
2.2.4. Tris[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)phenyl]amine (2c)
2. Experimental
Following general procedure A, 1c (1.92 g, 4.0 mmol), n-
BuLi (6 mL, 13.2 mmol) and 2-isopropoxy-4,4,5,5-tetramethyl-
[1,3,2]dioxaborolane (2.46 g, 13.2 mmol) were stirred in dry THF
(50 mL) overnight. Silica gel column chromatography afforded 2c
as white solids (1.60 g, 64%). 1H NMR (300 MHz, CDCl3): ı = 7.69 (d,
J = 8.4 Hz, 6H), 7.09 (d, J = 8.4 Hz, 6H), 1.34 ppm (s, 36H).
2.1. Materials & methods
All reagents were obtained from J&K, Aldrich, Acros and
TCI Chemical Co., and used as received unless otherwise speci-
fied. The bromo substituted triphenyl amine derivatives, namely
p-bromo-N,N-dimethoxyphenylaniline (1a), 4-bromo-N,N-bis(4-
were prepared following the reported procedures [60–62].
Tetrakis(triphenylphosphine)palladium(0) ((PPh3)4Pd0) was syn-
thesized in our lab. 6-Bromo substituted anthraquinone imide 4
was prepared following the previously reported procedure with
slight modification of the N-alkyl chain [63].
2.2.5. General procedure B for synthesis of
triphenylamine-anthraquinone imide product
To a mixture of 6-bromo substituted anthraquinone imide 4,
Na2CO3 and Pd(PPh3)4, compound 2, toluene, ethanol and water
were added under nitrogen. The reaction mixture was heated
to reflux and kept for 6 h. After cooled to room temperature,
the water layer was extracted with dichloromethane and the
combined organic layer was dried over MgSO4. Volatile solvent
was removed under reduced pressure. Then, the raw product
was purified by silica gel column chromatography (petroleum
ether/dichloromethane 1:2) as solids.
1H NMR and 13C NMR spectra were measured on a Mercury
plus 300 (300 MHz) or Bruker ARX400 (400 MHz) spectrometer
at the ambient temperature with CDCl3 as the solvent. Chemical
shifts in 1H and 13C NMR were recorded in ppm with tetram-
ethylsilane (0 ppm) and CDCl3 (77 ppm) as standards, respectively.
High-resolution mass spectra were recorded on a Bruker APEX
IV Fourier transform ion cyclotron resonance mass spectrome-
ter. Elemental analyses were performed on an Elementar Vario
EL instrument. UV/Vis absorption spectra were recorded on a
Perkin–Elmer lambda 35 spectrophotometer. Diffuse reflectance
measurements on powders were carried out on a Shimadzu UV-
3100 UV/Vis/NIR spectrophotometer.
2.2.6. N-(1-hexylheptyl)-6-[4-[bis(4-
methoxyphenyl)amino]phenyl]-anthraquinone-2,3-dicarboxylic
imide (TPA-AQI)
Following general procedure B, compound 4 (0.59 g, 1.1 mmol),
Na2CO3 (0.40 g, 3.8 mmol), Pd(PPh3)4 (60 mg) and compound 2a
(0.57 g, 1.4 mmol) were refluxed in a mixture of benzene (15 mL),
ethanol (3 mL) and water (6 mL) under nitrogen. Silica gel column
chromatography afforded the product TPA-AQI (0.47 g, 56%) as red
solids. 1H NMR (400 MHz, CDCl3): ı = 8.77 (s, 2H), 8.53 (d, J = 2.0 Hz,
1H), 8.38 (d, J = 8.4 Hz, 1H), 8.04 (q, J1 = 8.4, J2 = 2.0 Hz, 1H), 7.59 (d,
J = 8.8 Hz, 2H), 7.14 (d, J = 8.8 Hz, 4H), 7.02 (d, J = 8.4 Hz, 2H), 6.90 (d,
J = 9.2 Hz, 4H), 4.32–4.23 (m, 1H), 3.83 (s, 6H), 2.14–2.05 (m, 2H),
1.78–1.70 (m, 2H), 1.32–1.23 (m, 16H), 0.86 ppm (t, J = 6.8 Hz, 6H);
13C NMR (100 MHz, CDCl3): ı = 182.0, 181.1, 167.0, 156.5, 150.0,
147.3, 140.0, 138.4, 138.1, 135.6, 135.4, 133.5, 131.8, 130.8, 128.6,
2.2. Synthesis
2.2.1. General procedure A for synthesis of triphenylamine
substituted boronic ester (Scheme 1)
4-Bromo substituted triphenylamine was dissolved in dry
THF under nitrogen atmosphere and it was cooled to −78 ◦C.
n-BuLi was added with syringe and kept at −78 ◦C for one hour.
2-Isopropoxy-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane
was