The Journal of Organic Chemistry
Article
+
2
,6-Bis(3-methylsulfinylbenzo[b]thiophene)-4,8-bis-
22.6, 14.1; MS (MALDI-TOF) m/z 938 (M ); HR-MS (MALDI-MS)
1+
(
octaxyloxy)benzo[1,2-b;4,5-b′]dithiophene (3a). Compound 3a
m/z 855.9158 (M-Br) calcd for (C H S Br ) 855.91662.
38 35 4 3
was synthesized according to a similar procedure for compound 3b:
yield 62%; H NMR (300 MHz, CDCl , ppm) δ 8.72 (m, 2H), 7.90
m, 2H), 7.74 (s, 2H), 7.50 (m, 4H), 4.35 (t, 4H), 3.20 (s, 6H), 1.93
m, 4H), 1.67 (m, 4H), 1.33 (m, 16H), 0.89 (t, 6H); C NMR (100
MHz, CDCl , ppm) δ 144.7, 139.2, 138.6, 136.7, 133.2, 132.2, 131.1,
28.9, 126.3, 125.6, 124.1, 122.9, 122.5, 74.5, 40.4, 31.9, 30.6, 29.5,
9.4, 26.2, 22.7, 14.2; MS (MALDI-TOF) m/z 834 (M , 100); HR-
MS (MALDI-MS) m/z 834.2030, calcd for (C H O S )
Device Fabrication. The Si/SiO substrates were cleaned and
modified with octadecyltrichlorosilane (OTS) according to the
2
1
3
2
7
(
(
reported procedure. Transistor devices were fabricated in the top-
contact bottom-gate device configurations. Thin films were deposited
in high vacuum under different substrate temperatures to a thickness
of 65 nm. The Au source and drain electrodes were deposited through
a shadow mask by vacuum evaporation with a channle length 273 μm
and width 31 μm.
13
3
1
2
+
1
+
4
4
50
4 6
8
34.20279.
General Procedures for the Syntheses of 1a−c. 1a.
Compound 3a (510 mg, 0.6 mmol) was stirred with Eaton’s reagent
6 mL) at room temperature in the dark for 3 days. The mixture was
ASSOCIATED CONTENT
Supporting Information
■
*
S
(
Cyclic voltammograms, emission spectra, and characterization
poured into ice−water, and the brown solid collected by suction−
filtration was dried in vacuum. The solid was transferred to a dry 100
mL three-neck flask, and pyridine (100 mL) was added. The mixture
was refluxed for 1 day. After the mixture was cooled to room
temperature, the precipitate was collected by suction−filtration and
washed with CH Cl and acetone successively. Finally, recrystallization
AUTHOR INFORMATION
■
2
2
from CHCl and chlorobenzene in succession gave 1a as a yellow solid
3
1
(
°
(
150 mg, 32%): mp 226 °C; H NMR (400 MHz, CDCl CDCl (100
2 2
Author Contributions
C), ppm) δ 7.83 (t, 4H), 7.38 (t, 2H), 7.30 (t, 2H), 4.41 (t, 4H), 2.05
†
Y.X and X.Q. contributed equally.
q, 4H), 1.62 (q, 4H), 1.44 (q, 4H), 1.29−1.38 (m, 12H), 0.85 (t,
+
6
H); MS (MALDI-TOF) m/z 770 (M , 100). Anal. Calcd for
Notes
C H O S : C, 65.41; H, 5.49. Found: C, 65.29; H, 5.35.
The authors declare no competing financial interest.
42
42
2 6
1
b. Recrystallization from chlorobenzene several times gave yellow
1
crystals (270 mg, 40%): mp 335 °C; H NMR (400 MHz,
ACKNOWLEDGMENTS
■
CDCl CDCl (100 °C), ppm) δ 7.82 (t, 4H), 7.37 (t, 2H), 7.29 (t,
2
2
This work was financially supported by the National Natural
Sciences Foundation of China (21190031, 51303201) and the
National Basic Research Program of China (2011CB808405).
2
6
H), 3.28 (t, 4H), 1.90 (q, 4H), 1.64 (q, 4H), 1.39 (m, 8H), 0.89 (t,
H); MS (MALDI-TOF) m/z 682 (M , 100). Anal. Calcd for
+
C H S : C, 66.82; H, 5.02. Found: C, 66.77; H, 5.03.
38
34 6
1
c. Recrystallization from chlorobenzene several times gave yellow
1
crystals (120 mg, 24%): mp 260 °C; H NMR (400 MHz,
CDCl CDCl (100 °C), ppm) δ 7.77 (dd, 4H), 7.32 (t, 2H), 7.24
t, 2H), 3.23 (t, 4H), 1.87 (q, 4H), 1.61 (q, 4H), 1.41 (q, 4H), 1.27
m, 24H), 0.80 (t, 6H); MS (MALDI-TOF) m/z 821 (M−H , 100);
HR-MS(MALDI-MS) m/z 822.254 calcd for (C H S ) 822.25443.
Anal. Calcd for C H S : C, 70.02; H, 6.61. Found: C, 69.77; H, 6.55.
2
b′]dithiophene(4). A 25 mL Schlenk tube was charged with 2-
iodobenzo[b]thiophene (520 mg, 2 mmol), 2,6-bis(trimethyltin)-4,8-
bis(hexyl)benzo[1,2-b;4,5-b′]dithiophene (684 mg, 1.0 mmol), and
Pd(PPh ) (115 mg, 0.1 mmol). The mixture was purged under
REFERENCES
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2
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(
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(
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4
T. M.; Morpurgo, A. F. Appl. Phys. Lett. 2003, 83, 4345−4347.
nitrogen atmosphere, and 10 mL of DMF was injected. The mixture
was stirred overnight at 80 °C. After being cooled to room
temperature, the mixture was poured into water and extracted with
CH Cl . The combined organic phase was dried over MgSO , and the
(
c) Watanabe, M.; Chang, Y. J.; Liu, S.-W.; Chao, T.-H.; Goto, K.;
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P.; Bao, Z.; Aspuru-Guzik, A. Nat. Commun. 2011, 2, 437. (g) Niimi,
2
2
4
residue was purified by recrystallization from CH Cl to obtain 4 as a
yellow solid 450 mg (yield 72%): H NMR (400 MHz,
CDCl CDCl (100 °C), ppm) δ 7.73 (dd, 4H), 7.69 (d, 2H), 7.53
s, 2H), 7.48 (s, 2H), 7.27 (t, 4H), 3.10 (t, 4H), 1.52 (m, 4H), 1.47
3
1
2
2
(
(
(
(
m, 4H), 1.33 (m, 8H), 0.86 (t, 6H); MS (MALDI-TOF) m/z 622
+
M , 100); HR-MS(MALDI-MS) m/z 622.1854, calcd for
1+
C H S ) 622.18509.
38
38 4
2
,6-Bis(3-bromobenzo[b]thiophene)-3,7-dibromo-4,8-bis-
(
hexyl)benzo[1,2-b;4,5-b′]dithiophene (5). A 250 mL flask was
(
(
charged with compound 4 (312 mg, 0.5 mmol) and 150 mL of
CH Cl under N . Br (320 mg, 2 mmol) in 10 mL of CH Cl was
2
2
2
2
2
2
added dropwise at 0 °C. The reaction mixture was warmed to room
temperature and stirred overnight. The mixture was treated with
saturated Na S O aqueous solution and extracted with CHCl . The
organic phase was concentrated under vacuum evaporation, and the
precipitate was filtered and washed of acetone and CH Cl successively
to obtain 5 as a yellow solid (yield, 420 mg. 89%): H NMR (300
MHz, CDCl , ppm) δ 7.92 (dd, 2H), 7.85(dd, 2H), 7.50 (m, 4H), 3.60
t, 4H), 1.87 (m, 4H), 1.55(m, 4H), 1.36 (m, 8H), 0.89 (t, 6H);
NMR (100 MHz, CDCl , ppm) δ 139.7, 139.3, 138.0, 131.3, 131.2,
2
2
3
3
2
2
1
3
13
(
C
3
1
30.2, 126.3, 125.4, 124.0, 122.3, 111.4, 108.9, 31.5, 31.4, 30.9, 29.6,
1
143
dx.doi.org/10.1021/jo4025607 | J. Org. Chem. 2014, 79, 1138−1144