Article
4,40-Bis[(p-(2-thienylethenyl)phenyl)phenylamino]biphenyl (3).
Chem. Mater., Vol. 22, No. 23, 2010 6447
temperature, after which the resulting mixture was poured into
methanol and the precipitate was filtered off. The resulted
polymer was dissolved in 15 mL of chloroform. The solution
was filtered through a 0.45-μm PTFE filter, concentrated, and
precipitated from methanol to yield the polymer as a black solid
To a solution of 7.0 g (10 mmol) of compound 2 and 5.2 g (22.0
mmol) of diethyl (2-methylthiophene)-phosphonate in 80 mL of
dry THF was added 22.0 mL of 1 M potassium tert-butoxide
methanol solution. The reaction mixture was stirred overnight
at room temperature and then was diluted with dichloro-
methane and water. The two phases were separated, and the
water phase was extracted twice with dichloromethane. The
combined organic extracts were washed three times with water,
dried over magnesium sulfate, concentrated under reduced
pressure, and purified with column chromatography (silica gel,
petroleum ether/dichloromethane (3/1)) to give 7.5 g of yellow-
ish compound 3 with a yield of 87%. 1H NMR (CDCl3, ppm):
7.46 (d, 4H), 7.35 (d, 8H), 7.18-7.12 (m, 8H), 7.08-7.00 (m,
12H), 6.91(d, 2H). 13C NMR (CDCl3, ppm): 146.58, 146.52,
146.09, 143.11, 135.36, 132.33, 131.91, 130.00, 127.66, 127.62,
127.58, 127.32, 125.76, 125.67, 124.59, 124.06, 120.67, 115.45.
Anal. Calcd. for (C48H34Br2N2S2) (%): C, 66.82; H, 3.944; N,
3.248; S, 7.425. Found (%): C, 65.96; H, 3.752; N, 3.127; S,
6.624.
4,40-Bis[(p-(5-formyl-2-thienylethenyl)phenyl)phenylamino]biphenyl
(M4). Compound 3 (7.0 g, 8.1 mmol) was dissolved in 50 mL of
dry DMF. POCl3 (30 mL, 322 mmol) was added dropwise to the
mixture at 0 °C. The reaction mixture was allowed to warm to 50 °C
and stirred for 2 h. After cooling to room temperature, the
mixture was poured into water, neutralized with sodium carbo-
nate, and extracted with dichloromethane. The combined or-
ganic phases were washed with water and brine and then dried
over magnesium sulfate, and the solvent was removed under
reduced pressure. The crude product was purified using column
chromatography (silica gel, petroleum ether/dichloromethane
(2/1)) to yield 4.9 g (66%) of monomer M4. 1H NMR (CDCl3,
ppm): 9.84 (s, 2H), 7.73-7.71 (d, 2H), 7.50-7.47 (d, 4H),
7.40-7.37 (m, 8H), 7.16-7.00 (m, 18H). 13C NMR (CDCl3,
ppm): 182.52, 152.90, 147.76, 146.20, 145.88, 141.18, 137.37,
135.69, 132.48, 132.33, 130.32, 130.04, 128.06, 127.71, 126.14,
124.96, 123.35, 119.32, 116.09. Anal. Calcd. for (C48H34Br2-
N2S2) (%): C, 65.36; H, 3.704; N, 3.050; S, 6.972. Found (%): C,
65.00; H, 3.436; N, 3.025; S, 6.002.
1
(88 mg, 83%). H NMR (CDCl3, ppm): 8.14-8.10 (m, 2H),
7.72-7.65 (m, 5H), 7.59-7.56 (m, 3H), 7.50-7.41 (m, 4H),
7.33-7.31 (m, 3H), 7.22-7.20 (m, 3H), 7.13-7.07 (m, 3H), 4.26
(m, 2H), 2.17 (m, 1H), 1.44-1.26 (m, 8H), 0.96-0.86 (m, 6H).
GPC (THF, polystyrene standard): Mn = 2.7 kg/mol, Mw = 7.3
kg/mol, PDI = 2.7.
EH-PCzDTA. Pyridine (0.5 mL) was added to a solution of
EH-PCzCHO (100 mg, 0.15 mmol of the repeating unit) and 1,
3-diethyl-2-thiobarbituric acid (600 mg, 3 mmol) in 10 mL of
chloroform. The mixture solution was stirred in darkness for 36 h
at room temperature, after which the resulting mixture was
poured into methanol and the precipitate was filtered off. The
resulted polymer was dissolved in 15 mL of chloroform. The
solution was filtered through a 0.45-μm PTFE filter, concen-
trated, and precipitated from methanol to yield the polymer as a
black solid (101 mg, 81%). 1H NMR (CDCl3, ppm): 8.63 (s, 1H),
8.15-8.12 (m, 2H), 7.81-7.80 (m, 1H), 7.71-7.66 (m, 4H),
7.59-7.57 (m, 2H), 7.51-7.40 (m, 4H), 7.34-7.31 (m, 3H),
7.24-7.16 (m, 4H), 7.13-7.08 (m, 2H), 4.64-4.57 (m, 4H), 4.27
(m, 2H), 2.18 (m, 1H), 1.44-1.24 (m, 14H), 0.97-0.86 (m, 6H).
GPC (THF, polystyrene standard): Mn = 2.7 kg/mol, Mw =
6.1 kg/mol, PDI = 2.3.
C17-PCzCHO. C17-PCzCHO was synthesized according to
a procedure similar to that for EH-PCzCHO with respective
monomers. 1H NMR (CDCl3, ppm): 9.86 (s, 1H), 8.16-8.13 (m,
2H), 7.79-7.62 (m, 7H), 7.47-7.41 (m, 4H), 7.34-7.32 (d, 3H),
7.24-7.22 (d, 2H), 7.15-7.07 (m, 4H), 4.69 (s, 1H), 2.38 (m, 2H),
2.00 (m, 2H), 1.27-1.15 (m, 24H), 0.82 (t, 6H). GPC (THF,
polystyrene standard): Mn = 7.9 kg/mol, Mw = 15.5 kg/mol,
PDI=2.0.
C17-PCzDCN. C17-PCzDCN was synthesized according to a
procedure similar to that for EH-PCzDCN. 1HNMR(CDCl3,ppm):
8.15 (s, 2H), 7.77-7.60 (m, 8H), 7.47-7.44 (m, 4H), 7.34-7.32 (m,
3H), 7.25-7.15 (m, 6H), 4.68 (s, 1H), 2.40 (m, 2H), 2.00 (m, 2H),
1.26-1.14 (m, 24H), 0.79 (t, 6H). GPC (THF, polystyrene standard):
Mn = 7.4 kg/mol, Mw = 12.5 kg/mol, PDI=1.7.
EH-PCzCHO. In a 50-mL two-necked round-bottomed
flask, 531 mg (1.0 mmol) of monomer M1, 539 mg (1.0 mmol)
of M3, and 10 mg of Pd(PPh3)4 were dissolved in a mixture of 10
mL of degassed toluene, 10 mL of distilled THF and 4 mL of
degassed aqueous sodium carbonate (2.0 M). The solution was
flushed with argon for 15 min. The mixture was refluxed with
vigorous stirring in darkness for 24 h under an argon atmo-
sphere. After cooling to room temperature, the mixture was
poured into methanol. The precipitated material was collected
by filtration through a funnel. After washing with acetone for
24 h in a Soxhlet apparatus to remove oligomers and catalyst
residues, the resulting material was dissolved in 30 mL of
chloroform. The solution was filtered with a 0.45-μm PTFE
filter, concentrated, and precipitated from methanol to yield
EH-PCzCHO as an orange solid (387 mg, 59%). 1H NMR
(CDCl3, ppm): 9.85 (s, 1H), 8.16-8.13 (m, 2H), 7.70-7.64 (m,
5H), 7.59-7.56 (m, 2H), 7.51-7.40 (m, 4H), 7.33-7.31 (m, 3H),
7.22-7.20 (m, 2H), 7.14- 7.12 (m, 4H), 4.26 (m, 2H), 2.16 (m,
1H), 1.45-1.28 (m, 8H), 0.97-0.86 (m, 6H). GPC (THF,
polystyrene standard): Mn = 2.7 kg/mol, Mw = 7.1 kg/mol,
PDI=2.6.
C17-PCzDTA. C17-PCzDTA was synthesized according to a
procedure similar to that for EH-PCzDTA. 1H NMR (CDCl3,
ppm): 8.63 (s, 1H), 8.16 (s, 2H), 7.78-7.61 (m, 7H), 7.47-7.39
(m, 4H), 7.35-7.32 (m, 3H), 7.26-7.16 (m, 6H), 4.60-4.58 (m,
5H), 2.37 (m, 2H), 1.99 (m, 2H), 1.79 (t, 6H), 1.26-1.14 (m,
24H), 0.80 (t, 6H). GPC (THF, polystyrene standard): Mn = 5.6
kg/mol, Mw = 6.7 kg/mol, PDI = 1.2.
C17-PCzDCHO. C17-PCzDCHO was synthesized according
to a procedure similar to that for EH-PCzCHO with respective
monomers. 1H NMR (CDCl3, ppm): 9.90 (s, 2H), 8.16 (m, 2H),
7.70-7.47 (m, 18H), 7.31-7.26 (m, 6H), 7.17-7.00 (m, 12H),
4.70 (m, 1H), 2.39 (m, 2H), 2.00 (m, 2H), 1.17-1.01 (m, 24H),
0.82 (t, 6H). GPC (THF, polystyrene standard): Mn = 13.1 kg/
mol, Mw=29.4 kg/mol, PDI = 2.3.
C17-PCzDDCN. C17-PCzDDCN was synthesized according
to a procedure similar to that for EH-PCzDCN. 1H NMR
(CDCl3, ppm): 8.14 (s, 2H), 7.73 (s, 2H), 7.68-7.45 (m, 18H),
7.31-7.26 (m, 6H), 7.17-7.00 (m, 12H), 4.68 (m, 1H), 2.39 (m,
2H), 2.00 (m, 2H), 1.17-1.01 (m, 24H), 0.82 (t, 6H). GPC (THF,
polystyrene standard): Mn =13.7 kg/mol, Mw =27.2 kg/mol,
PDI = 2.0.
EH-PCzDCN. Pyridine (0.5 mL) was added to a solution of
EH-PCzCHO (100 mg, 0.15 mmol of the repeating unit) and
malononitrile (396 mg, 6.0 mmol) in 10 mL of chloroform. The
mixture solution was stirred in darkness for 36 h at room
C17-PCzDDTA. C17-PCzDDTA was synthesized according
to a procedure similar to that for EH-PCzDTA. 1H NMR