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(ppm): 7.55 (d, J = 5.4 Hz, 2H), 7.40 (d, J = 5.4 Hz, 2H), 4.83 (s,
4H).
4.16 (d, J = 5.1 Hz, 4H), 1.89−1.82(m, 2H), 1.62−1.52(m, 4H),
1.52−1.27 (m, 60H), 0.90−0.86 (m, 12H).
Dithieno[3′,2′:3,4;2″,3″:5,6]benzo[1,2-c][1,2,5]thiadiazole
(fDTBT). A mixture of diamine compound 4 (1.49 g, 6.77 mmol),
CH2Cl2 (40 mL), and Et3N (3.7 6 mL,27.1 mmol) was stirred until the
diamine compound 4 was dissolved. After the dropwise addition of
thionyl chloride (0.96 mL, 13.5 mmol), the mixture was refluxed for 5
h. Then, the mixture was concentrated under reduced pressure and
added with H2O (80 mL). After pH was adjusted to 2 by concentrated
HCl, the mixture was extracted with CH2Cl2 (3 × 70 mL). The
organic phase was combined, washed with H2O (2 × 50 mL), and
dried over Na2SO4. After filtration, the filtrate was concentrated, and
the residue was subjected to silica column chromatography using
petroleum ether/CH2Cl2 (1/1, v/v) as eluent, allowing to separate
4,8-Di(2-decyl)tetradecyloxybenzo[1,2-b;3,4-b′]dithiophene
(BDT24). Compound BDT24 was synthesized as colorless oil in a yield
of 51.6% following the similar method of BDT16. 1H NMR (300 MHz,
CDCl3) δ (ppm): 7.46 (d, J = 5.7 Hz, 2H), 7.36 (d, J = 5.7 Hz, 2H),
4.16 (d, J = 5.1 Hz, 4H), 1.89−1.82 (m, 2H), 1.62−1.27 (m, 80H),
0.90−0.86 (t, J = 6.6 Hz, 12H).
2,6-Bis(trimethyltin)-4,8-di(2-hexyl)decyloxybenzo[1,2-b;3,4-b′]-
dithiophene (Sn-BDT16-Sn). Compound BDT16 (0.70 g, 1.04 mmol)
and dry THF (20 mL) were added into a flask under an inert
atmosphere. The solution was cooled down to −78 °C and dropwise
added with n-butyllithium (2.93 mL, 1.6 M in n-hexane, 4.69 mmol).
After being warmed to room temperature and stirred for 2 h, the
reaction mixture was cooled to −78 °C again. Then, trimethyltin
chloride (5.0 mL, 1 M in n-hexane, 5.0 mmol) was added, and the
reaction mixture was allowed to naturally warm to room temperature
and stirred overnight. After quenched with water (100 mL), the
mixture was extracted with ether for three times. The combined
organic layer was washed with water and dried over anhydrous
Na2SO4. After filtration, the filtrate was concentrated under reduced
pressure, and the residue was recrystallized from isopropanol to give
0.45 g of compound Sn-BDT16-Sn as white needle in a yield of 43.3%.
1H NMR (300 MHz, CDCl3) δ (ppm): 7.51 (s, 2H), 4.18 (d, J = 3.9
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0.90 g of fDTBT as a yellow solid in a yield of 53.5%. H NMR (300
MHz, CDCl3) δ (ppm): 8.05 (d, J = 5.4 Hz, 2H), 7.56 (d, J = 5.4 Hz,
2H). 13C NMR (100 MHz, CDCl3) δ (ppm): 150.6, 135.5, 129.0,
125.4, 124.3. EI MS: 248 (100%).
5,8-Dibromodithieno[3′,2′:3,4;2″,3″:5,6]benzo[1,2-c][1,2,5]-
thiadiazole (Br-fDTBT-Br). To a mixture of compound fDTBT (0.40 g,
1.68 mmol), chloroform (14 mL), and acetic acid (14.5 mL) was
dropwise added with the solution of bromine (0.19 mL, 3.70 mmol) in
chloroform (1.9 mL) at 0 °C. After further addition of chloroform (50
mL), the mixture was refluxed for 5 h. Then, the reaction mixture was
cooled to room temperature and filtrated. The filtrate cake was
collected, dried, recrystallized from o-dichlorobenzene, allowing to
afford 0.55 g of compound Br-fDTBT-Br as a yellow needle solid in a
yield of 84.1%. 1H NMR (400 MHz, C2D2Cl4, 110 °C) δ (ppm): 8.01
(s, 2H). EI MS: 406 (100%). Anal. Calcd for C10H2Br2N2S3: C, 29.57;
H, 0.50; N, 6.90. Found: C, 29.73; H, 0.41; N, 7.14.
Hz, 4H), 1.86 (br, 2H), 1.64−1.29 (m, 48H), 0.90−0.87 (m, 12H),
0.44 (s, 18H). 13C NMR (100 MHz, CDCl3) δ (ppm): 143.20, 140.32,
133.82, 132.87, 127.93, 75.88, 39.18, 31.95, 31.40, 30.16, 29.81, 29.70,
29.39, 27.06, 27.00, 22.71, 22.68, 14.12, −8.40. Anal. Calcd for
C48H86O2S2Sn2: C, 57.84; H, 8.70. Found: C, 57.78; H, 8.70.
2,6-Bis(trimethyltin)-4,8-di(2-ethyl)hexyloxybenzo[1,2-b;3,4-b′]-
dithiophene (Sn-BDT8-Sn). Compound Sn-BDT8-Sn was synthesized
as white needle in a yield of 88.7% following the similar method of Sn-
4,8-Di(2-hexyl)decyloxybenzo[1,2-b;3,4-b′]dithiophene (BDT16).
Benzo[1,2-b:4,5-b′]dithiophene-4,8-dione (0.56 g, 2.5 mmol), zinc
powder (0.41 g, 6.4 mmol), and water (7.5 mL) were put into a 100
mL flask under the protection of argon. Then NaOH (1.50 g, 37.5
mmol) was added into the mixture. The mixture was well stirred and
heated to reflux for 1 h. During the reaction, the color of the mixture
changed from yellow to red and then to orange. Afterward, 2-
hexyldecyl bromide (2.35 g, 7.7 mmol) and a catalytic amount of
tetrabutylammonium bromide (0.05 g, 0.15 mmol) were added into
the flask. After being refluxed for 2 h, the reaction mixture was poured
into cold water and extracted with diethyl ether. The organic layer was
combined and dried over anhydrous Na2SO4. After filtration, the
filtrate was concentrated under reduced pressure, and the residue was
subjected to silica column chromatography using hexane as eluent,
allowing to separate 1.20 g of compound BDT16 as colorless oil in a
yield of 71.6%. 1H NMR (300 MHz, CDCl3) δ (ppm): 7.47 (d, J = 5.7
Hz, 2H), 7.36 (d, J = 5.7 Hz, 2H), 4.16 (br, 4H), 1.86 (br, 2H), 1.61
(br, 4H), 1.53−1.26 (m, 44H), 0.89 (br, 12H).
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BDT16-Sn. H NMR (300 MHz, CDCl3) δ (ppm): 7.52 (s, 2H), 4.19
(d, J = 3.9 Hz, 4H), 1.84−1.41 (m, 18H), 1.03 (t, J = 6.0 Hz, 6H), 0.95
(t, J = 6.0 Hz, 6H), 0.45 (s, 18H). 13C NMR (100 MHz, CDCl3) δ
(ppm): 143.22, 140.35, 133.83, 132.87, 127.95, 75.60, 40.65, 30.52,
29.23, 23.89, 23.16, 14.17, 11.34, −8.38. Anal. Calcd for
C32H54O2S2Sn2: C, 49.76; H, 7.05. Found: C, 49.56; H, 6.97.
2,6-Bis(trimethyltin)-4,8-di(3,7-dimethyl)octyloxybenzo[1,2-b;3,4-
b′]dithiophene (Sn-BDT10-Sn). Compound Sn-BDT10-Sn was synthe-
sized as white needle in a yield of 61.8% following the similar method
of Sn-BDT16-Sn. 1H NMR (300 MHz, CDCl3) δ (ppm): 7.51 (s, 2H),
4.39−4.28 (m, 4H), 1.97−1.19 (m, 20H), 0.99 (t, J = 6.9 Hz, 6H),
0.87 (t, J = 6.6 Hz, 12H), 0.44 (s, 18H). 13C NMR (100 MHz, CDCl3)
δ (ppm): 143.10, 140.46, 133.95, 132.93, 127.98, 71.89, 39.28, 37.62,
37.31, 29.75, 27.97, 24.71, 22.71, 22.61, 19.72, −8.34. Anal. Calcd for
C36H62O2S2Sn2: C, 52.19; H, 7.54. Found: C, 52.32; H, 7.55.
2,6-Bis(trimethyltin)-4,8-di(2-butyl)octyloxybenzo[1,2-b;3,4-b′]-
dithiophene (Sn-BDT12-Sn). Compound Sn-BDT12-Sn was synthe-
sized as white needle in a yield of 73.8% following the similar method
of Sn-BDT16-Sn. 1H NMR (300 MHz, CDCl3) δ (ppm): 7.51 (s, 2H),
4.18 (d, J = 3.9 Hz, 4H), 1.86 (br, 2H), 1.67 (br, 4H), 1.56−1.26 (m,
28H), 0.97−0.90 (m, 12H), 0.44 (s, 18H). 13C NMR (100 MHz,
CDCl3) δ (ppm): 143.20, 140.33, 133.81, 132.88, 127.93, 75.87, 39.16,
31.95, 31.39, 31.09, 29.81, 29.25, 27.00, 23.16, 22.71, 14.18, 14.13,
−8.41. Anal. Calcd for C40H70O2S2Sn2: C, 54.31; H, 7.98. Found: C,
54.49; H, 8.02.
2,6-Bis(trimethyltin)-4,8-di(2-octyl)dodecyloxybenzo[1,2-b;3,4-
b′]dithiophene (Sn-BDT20-Sn). Compound Sn-BDT20-Sn was synthe-
sized as white needle in a yield of 82.1% following the similar method
of Sn-BDT16-Sn. 1H NMR (300 MHz, CDCl3) δ (ppm): 7.51 (s, 2H),
4.17 (d, J = 3.9 Hz, 4H), 1.85 (br, 2H), 1.64−1.27 (m, 64H), 0.89 (t, J
= 6.3 Hz, 12H), 0.44 (s, 18H). 13C NMR (100 MHz, CDCl3) δ
(ppm): 143.20, 140.30, 133.82, 132.86, 127.93, 75.91, 39.18, 31.92,
31.39, 30.17, 29.74, 29.71, 29.67, 29.39, 29.36, 27.05, 22.68, 14.11,
−8.39. Anal. Calcd for C56H102O2S2Sn2: C, 60.65; H, 9.27. Found: C,
61.04; H, 9.24.
4,8-Di(2-ethyl)hexyloxybenzo[1,2-b;3,4-b′]dithiophene (BDT8).
Compound BDT8 was synthesized as colorless oil in a yield of
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80.9% following the similar method of BDT16. H NMR (300 MHz,
CDCl3) δ (ppm): 7.48 (d, J = 5.4 Hz, 2H), 7.36 (d, J = 5.4 Hz, 2H),
4.14 (d, J = 4.5 Hz, 4H), 1.85−1.26 (m, 18H), 0.98 (t, J = 5.4 Hz, 6H),
0.88 (t, J = 5.4 Hz, 6H).
4,8-Di(3,7-dimethyl)octyloxybenzo[1,2-b;3,4-b′]dithiophene
(BDT10). Compound BDT10 was synthesized as colorless oil in a yield
of 95.5% following the similar method of BDT16. 1H NMR (300 MHz,
CDCl3) δ (ppm): 7.48 (d, J = 5.7 Hz, 2H), 7.36 (d, J = 5.7 Hz, 2H),
4.32 (br, 4H), 1.97−1.15 (m, 20H), 0.97 (d, J = 6.3 Hz, 6H), 0.88 (t, J
= 6.6 Hz, 12H).
4,8-Di(2-butyl)octyloxybenzo[1,2-b;3,4-b′]dithiophene (BDT12).
Compound BDT12 was synthesized as colorless oil in a yield of
1
79.6% following the similar method of BDT16. H NMR (300 MHz,
CDCl3) δ (ppm): 7.46 (d, J = 5.7 Hz, 2H), 7.37 (d, J = 5.7 Hz, 2H),
4.17 (br, 4H), 1.86 (br, 2H), 1.63 (br, 4H), 1.53−1.26 (m, 28H), 0.90
(m, 12H).
4,8-Di(2-octyl)dodecyloxybenzo[1,2-b;3,4-b′]dithiophene
(BDT20). Compound BDT20 was synthesized as colorless oil in a yield
of 49.2% following the similar method of BDT16. 1H NMR (300 MHz,
CDCl3) δ (ppm): 7.46 (d, J = 5.7 Hz, 2H), 7.36 (d, J = 5.7 Hz, 2H),
2,6-Bis(trimethyltin)-4,8-di(2-decyl)tetradecyloxybenzo[1,2-b;3,4-
b′]dithiophene (Sn-BDT24-Sn). Compound Sn-BDT24-Sn was synthe-
sized as white needle in a yield of 90.0% following the similar method
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dx.doi.org/10.1021/ma401298g | Macromolecules 2013, 46, 7920−7931