Supporting Information for
Linear -Conjugated Polymers Containing
2,4,6-tris(thiophen-2-yl)-1,3,5-triazine Unit: Synthesis and Optical
Properties
Li Zou, Yang Fu, Xiaobing Yan, Xingguo Chen*, Jingui Qin
Department of Chemistry, Hubei Key Laboratory on Organic and Polymeric Opto-electronic
Materials, Wuhan University, Wuhan 430072, China. xgchen@whu.edu.cn
Syntheses for some known monomers as in references
1,4-Dibromo-2,5-bisdodecyloxybenzene
(1)
[1].
To
a
solution
of
1,4-bisdodecyloxybenzene (1.34 g, 3 mmol) in 40 mL CCl4 was slowly added Br2 (12
mmol, 0.6 mL) in 20 mL CCl4. Then the mixture was stirred at 80 C for 24 h.
After completion the solvent was evaporated, and the crude product was dissolved in
CHCl3 and washed with the saturated solution of Na2S2O6 (60 mL2).
The organic
layer was dried over anhydrous MgSO4, and concentrated under vacuum. The crude
product was recrystallized from ethanol. And white solid was obtained. (1.75 g, 97 %
yield).
1
H-NMR (300Mz, CDCl3): δ 0.902 (t, 6H), 1.285 (b, 32H), 1.495 (m, 4H),
1.817 (m, 4H), 3.952 (t, 4H), 7.080 (s, 2H).
2,7-Dibromo-9-dodecylcarbazole
(2)
[2].
To
a
solution
of
2,7-dibromo-9H-carbazole (4.1 g, 12.5 mmol ) was added NaOH (0.5 g, 12.5 mmol).
The mixture was allowed to stir for 20min, and then 1-bromododecane (4.67g，18.75
mmol) was added. After stirring at room temperature for 6 h, the reaction mixture
was poured into 150 mL H2O, extracted with CHCl3 (200 mL2). The organic layer
was dried over anhydrous MgSO4 and concentrated under vacuum. The white solid
product was obtained by chromatography with petroleum ether as an eluent. (5.35 g,
84% yield). 1H-NMR (300Mz, CDCl3,δ): 0.892 (t, 3H), 1.238 (m, 18H), 1.819 (m,
2H), 4.245 (t, 2H), 7.279 (d, 2H), 7.530 (d, 2H), 8.134 (s, 1H).
2,7-Dibromo-9,9-dihexylfluorene (3) [3]. To a solution of 2,7-dibromo-9H-fluorene
(3.24 g, 10 mmol ) in 50 mL DMF was added KOH (11.2 g, 0.2 mol) and KI (1.0 g,
6.0 mmol). The mixture was allowed to stir for 30 min, and then 8.5 mL
1-bromohexane (9.9 g，60 mmol) was added. After stirring at room temperature for 24
h, the reaction mixture was poured into 500 mL H2O, extracted with CHCl3 (200
mL2). The organic layer was dried over anhydrous MgSO4 and concentrated under
vacuum. The product was obtained by flash chromatography with petroleum ether as
an eluent. The crude product was recrystallized from ethanol. And white crystal
product was obtained. (4.42 g, 87 % yield). 1H-NMR (300Mz, CDCl3,δ): 0.589 (m,
4H), 0.794 (t, 6H), 1.056-1.170 (m, 12H), 1.893-1.948 (m, 4H), 7.425-7.522 (m, 6H).
2,5-Bis-dodecyloxy-1,4-diethynyl-benzene (4) [4].
(Trimethylsilyl)acetylene (1
mL, 6 mmol), 1 (1.21 g, 2 mmol), Pd(PPh3)4 (46 mg, 0.04 mmol, 2 %), CuI (8 mg,
0.04 mmol, 2 %) and PPh3 (10mg, 0.04 mmol, 2 %) was dissolved in TEA (30 mL) at
Ar atmosphere. The reaction was stirred at 50 C for 36 h. The solvent was removed
under vacuum. The crude residue was purified by flash chromatography with the
mixture of petroleum ether/CHCl3 (4/1) as an eluent to afford 0.79 g of light yellow
solid. Then the above product was dissolved in THF/MeOH (20 mL/10 mL). To the
solution was added 5N NaOH (0.8 mL, 4 mmol). The mixture was stirred at room
temperature for 1 h. 50 mL H2O was added and the mixture was extracted with CHCl3
(50 mL2). The organic layer was dried over anhydrous MgSO4 and concentrated
under vacuum. The residue was purified by flash chromatography with petroleum
ether / CHCl3 (4/1) as an eluent to afford 0.51 g (52 %) of yellow crystals. Further
purification was taken by recrystallized from hexane.
1
H-NMR (300Mz, CDCl3,δ):
0.803 (t, 6H), 1.183-1.223 (m, 32H), 1.378 (m, 4H), 1.741 (m, 4H), 3.249 (s, 2H),
3.878 (t, 4H), 6.851 (s, 2H).
2,7-diethynyl-9-Dodecylcarbazole (5) [5]. (Trimethylsilyl)acetylene (1.4 mL, 10
mmol), 2 (1.974 g, 4 mmol), Pd(PPh3)4 (92 mg, 0.08 mmol), CuI (16 mg, 0.08 mmol,
2%) and PPh3 (20 mg, 0.08 mmol, 2%) was dissolved in TEA (30 mL) at Ar
atmosphere. The mixture was stirred at 50 C for 36 h. The solvent was removed
under vacuum. The crude residue was purified by flash chromatography using
petroleum ether / CHCl3 (6/1) as an eluent to afford 2.28 g of a light yellow solid.
Then the above product was dissolved in THF/MeOH (20 mL/10 mL). To the solution
was added 5 N NaOH (1.6 mL, 8 mmol). The reaction was stirred at room
temperature for 1 h. Then 50 mL H2O was added and the mixture was extracted with
CHCl3 (50 mL2). The organic layer was dried over anhydrous MgSO4 and
concentrated under vacuum.
The residue was purified by flash chromatography with
petroleum ether/CHCl3 (6/1) as an eluent to afford 1.34 g (87 %) of light yellow
crystals.
1
H-NMR (300Mz, CDCl3): δ 0.872 (t, 3H), 1.223 (m, 18H), 1.839 (m, 2H),
3.081 (s, 2H), 4.263 (t, 2H), 7.347 (d, 2H), 7.615 (d, 2H), 8.216 (s, 1H).
2,7-Diethynyl-9,9-dihexylfluorene (6) [6]. (Trimethylsilyl)acetylene (1.4 mL, 10
mmol), 3 (1.968 g, 4 mmol), Pd(PPh3)4 (92 mg, 0.08 mmol, 2%), CuI (16mg, 0.08
mmol, 2%) and PPh3 (20 mg, 0.08 mmol, 2%) was dissolved in TEA (30mL) at Ar
atmosphere. The mixture was stirred at 50 C for 36 h. The solvent was removed
under vacuum. The crude residue was purified by flash chromatography with
petroleum ether / CHCl3 (4/1) to afford 2.01 g of a light yellow solid. Then the above
product was dissolved in THF/MeOH (20 mL/10 mL). To the solution was added 5N
NaOH (1.6 mL, 8 mmol). The mixture was stirred at room temperature for 1h. 50mL
H2O was added and the mixture was extracted with CHCl3 (50mL2). The organic
layer was dried over anhydrous MgSO4, and concentrated under vacuum. The residue
was purified by flash chromatography with petroleum ether/CHCl3 (4/1) as an eluent
to afford 1.42 g (93 %) of white solid. 1H-NMR (300Mz, CDCl3, δ): 0.549 (m, 4H),
0.756 (t, 6H), 1.004-1.112 (m, 12H), 1.898-1.953 (m, 4H), 3.46 (s, 2H), 7.449-7.485
(m, 4H), 7.610 (d, 2H).
2,4,6-tri-(2-thienyl)-1,3,5-triazine (7) [7]. To a vigorously stirred solution of
trifluoromethylsulfonic acid (0.50 g, 30 mmol) in 5 mL dry CHCl3 was slowly added
thienylnitrile (3.28 g, 30 mmol) in 50 mL dry CHCl3 over a course of 1h at 0 C under
atmosphere of nitrogen. After stirring for another 1 h, the mixture was warmed to
room temperature and stirred for another 24 h. And then it was poured into 100 mL
water containing 5mL NH3·H2O. The organic layer was separated and the aqueous
layer was extracted with CHCl3. The combined organic layer was dried over
anhydrous MgSO4 and concentrated under vacuum. The pine needle crystal was
obtained. (2.75 g, 85 % yield). 1H-NMR (300Mz, CDCl3, δ): 7.21 (t, 3H), 7.62 (d, 3H),
8.27 (d, 3H).
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