JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
hydroxide (3.18 g, 56.6 mmol), and 1,10-phenanthroline
(0.32 g, 1.77 mmol) in toluene (120 mL) was stirred at
125 C for 12 h under nitrogen atmosphere. After cooling to
room temperature, the mixture was extracted with ethyl
acetate (50 mL ꢃ 3) and brine water, and then the combined
organic layers dried over anhydrous MgSO4 and filtered, and
the solvent was removed by evaporation. The crude product
was purified by column chromotography on silica gel using
hexane as eluent to afford the desired product 4 as a light-
yellow solid (3.1 g, 48%).
5-[4-[Bis(2-bromo-9,9-dihexyl-7-fluorenyl)amino]
styryl]thiophene-2-carbaldehyde (M4)
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To a solution of M3 (1.67 g, 1.63 mmol) and DMF (0.3 g,
4.08 mmol) in 1,2-dichloroethane was added POCl3 (0.63 g,
4.08 mmol) by syringe at 0 ꢀC. The mixture was stirred at
ꢀ
90 C for 12 h. After being cooled to room temperature, the
solution was poured into NaHCO3 solution slowly and stirred
for 30 min. The mixture was extracted with CH2Cl2 and
water; the combined organic layers were dried over MgSO4,
evaporated, and purified with column chromatography [silica
gel, hexane/ethyl acetate (20/1) as eluent] to yield M4 as
orange solid (2.73 g, 89%).
1H NMR (300 MHz, CDCl3): d 7.44–7.32 (m, 8H), 7.20–7.15
(m, 2H), 7.06–7.04 (m, 4H), 6.97–6.92 (m, 3H), 1.76 (t, J ¼
5.9 Hz, 8H), 1.09–1.04 (m, 24H), 0.78–0.70 (m, 12H), 0.56
(m, 8H).
MS (FAB) m/z: 1052. 1H NMR (300 MHz, CDCl3): d 9.85 (s,
1H), 7.66 (d, J ¼ 3.6 Hz, 1H), 7.56–7.53 (m, 2H), 7.50–7.42
(m, 6H), 7.38–7.35 (m, 2H), 7.15–7.03 (m, 9H), 1.87–1.83
(m, 8H), 1.17–1.07 (m, 24H), 0.86–0.79 (m, 11H), 0.66 (m,
9H): 13C NMR (75 MHz, CDCl3): d 182.2, 152.9, 152.7, 151.8,
148.4, 146.5, 140.9, 139.6, 137.3, 135.7, 132.3, 129.9, 129.4,
127.8, 125.9, 123.8, 122.4, 120.5, 120.4, 119.3, 118.7, 55.2,
40.0, 31.4, 29.5, 23.7, 22.5, 14.0. Anal. Calcd. for
4-[Bis(2-bromo-9,9-dihexyl-7-fluorenyl)
amino]benzaldehyde (5)
To a solution of 4 (0.95 g, 1.04 mmol) and N,N-dimethylfor-
mamide (DMF) (0.76 g, 10.4 mmol) in 1,2-dichloroethane
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was added POCl3 (1.59 g, 10.4 mmol) by syringe at 0 C. The
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mixture was stirred at 90 C for 12 h. After being cooled to
C63H73Br2NOS: C, 71.92; H, 6.99; N, 1.33. Found: C, 71.86; H,
room temperature, the solution was poured into NaHCO3 so-
lution slowly and stirred for 30 min. The mixture was
extracted with CH2Cl2 and water; the combined organic
layers were dried over MgSO4, evaporated, and purified with
column chromatography [silica gel, hexane/ethyl acetate
(20/1) as eluent] to yield 5 as yellow liquid (0.77 g, 79%).
7.27; N, 1.36.
General Procedure for the Synthesis of Conjugated
Precursor Polymers via Stille Coupling Reaction
Into a 25-mL of two-neck flask, 1 equiv of dibromo mono-
mers (M1–M4) and 1 equiv of M5, Pd2(dba)3 (4 mol %) and
tri(o-tolyl)phosphine (32 mol %) were added in anhydrous
toluene and deoxygenated with nitrogen for 30 min. The
MS (FAB) m/z: 944. 1H NMR (300 MHz, CDCl3): d 9.84 (s,
1H), 7.70 (d, J ¼ 8.7 Hz, 2H), 7.60 (d, J ¼ 8.1 Hz, 2H), 7.52–
7.43 (m, 6H), 7.20 (m, 2H), 7.12–7.08 (m, 4H), 1.90–1.85 (m,
8H), 1.81–1.06 (m, 24H), 0.84–0.76 (m, 12H), 0.66 (m, 8H);
13C NMR (75 MHz, CDCl3): d 190.3, 153.3, 153.0, 152.1,
145.6, 139.4, 137.2, 131.3, 130.1, 129.2, 126.1, 125.1, 120.9,
120.8, 120.7, 119.4.
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reaction mixture was stirred at 120 C for 3 days. After cool-
ing to room temperature, the solution was added into metha-
nol dropwise. The precipitate was collected by filtration and
washed by Soxhlet extraction with methanol, acetone, and
THF sequentially for 3 days. The Pd-thiol gel (Silicycle) was
added to above THF solution to remove the residual Pd cata-
lyst. After filtration and removal of the solvent, the polymer
was redissolved in THF again and added into methanol
to reprecipitate out. The purified polymer was collected by
filtration and dried under vacuum for 1 day.
7-Bromo-N-(2-bromo-9,9-dihexyl-7-fluorenyl)-9,9-dihexyl-
N-[4-[2-(thio-phen-2-yl)vinyl]phenyl]fluoren-2-amine (M3)
To a solution of 5 (0.3 g, 0.32 mmol) and diethyl (2-methyl-
thiophene)-phosphonate 6 (0.09 g, 0.39 mmol) in dry THF
(50 mL) was added potassium tert-butoxide methanol solu-
tion (1 M, 0.4 mL). The reaction mixture was stirred for 12 h
at room temperature and then was neutralized with 5% hy-
drochloric acid solution. 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 MgSO4, evaporated, and purified with col-
umn chromatography on silica gel using hexane/ethyl acetate
(20/1) as eluent to yield M3 as a yellow solid (0.26 g, 80%).
CPDT-co-TPA
Following the general polymerization procedure, M5 (659
mg, 0.905 mmol), M1 (463 mg, 0.905 mmol), Pd2(dba)3
(33.2 mg, 0.036 mmol), P(o-tolyl)3 (88.2 mg, 0.29 mmol),
and toluene (30 mL) were used in the polymerization, and
the polymer was obtained as a orange powder (0.34 g,
50%).
1H NMR (300 MHz, CDCl3): d 7.51–7.49 (m, 4H), 7.40–7.36
(m, 2H), 7.20–7.13 (m, 9H), 7.06–7.05 (m, 2H), 7.02–7.00
(m, 1H), 6.93–6.87 (m, 1H), 1.91 (m, 4H), 1.00–0.98 (m,
16H), 0.74 (m, 8H), 0.65 (t, J ¼ 7.2 Hz, 6H).
MS (FAB) m/z: 1024. 1H NMR (300 MHz, CDCl3): d 7.54–
7.51 (m, 2H), 7.48 (s, 1H), 7.45–7.41 (m, 5H), 7.36–7.33 (m,
2H), 7.17–7.15 (m, 3H), 7.11–6.97 (m, 7H), 6.92–6.87 (m,
1H), 1.85 (t, J ¼ 6.6 Hz, 8H), 1.18–1.07 (m, 25H), 0.84–0.78
(m, 11H), 0.66 (m, 8H); 13C NMR (75 MHz, CDCl3): d 152.8,
151.8, 147.3, 147.0, 143.2, 139.8, 135.4, 131.1, 129.9, 127.7,
127.6, 127.1, 126.0, 125.6, 123.9, 123.5, 123.2, 120.5, 120.4,
120.3, 119.0. Anal. Calcd. for C62H73Br2NS: C, 72.71; H, 7.18;
N, 1.37. Found: C, 72.87; H, 7.32; N, 1.31.
CPDT-co-TPACHO
Following the general polymerization procedure, M5 (333.5
mg, 0.458 mmol), M2 (246.9 mg, 0.458 mmol), Pd2(dba)3
(16.8 mg, 0.018 mmol), P(o-tolyl)3 (44.6 mg, 0.147 mmol),
and toluene (15 mL) were used in this polymerization, and
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