Synthesis and Properties of Thieno[3,2-b]thiophene Derivatives for Application of OFET Active Layer 33
16.0 Hz, CH CH), 7.16 (2H, d, J = 8.0 Hz, ArH),
crystals. mp 189–190◦C; 1H NMR (500 MHz, CDCl3)
7.18 (1H, s, ArH), 7.20 (1H, d, J = 5.0 Hz, ArH),
7.20 (1H, d, J = 16.0 Hz, CH CH), 7.34 (1H, d, J
= 5.0 Hz, ArH), 7.39 (2H, d, J = 8.0 Hz, ArH); 13C
NMR (126 MHz, CDCl3) δ 14.1, 22.7, 29.3, 31.4,
31.9, 35.8, 118.1, 119.7, 121.6, 126.3, 127.2, 128.5,
128.8, 134.2, 137.8, 139.5, 142.9, 145.5; IR (KBr)
3085, 2938, 1463, 949, 829, 698, 561 cm−1; EI-MS
(70 eV) m/z 354 (M+); Anal. Calcd For C22H28S2: C,
74.52; H, 7.39%. Found: C, 74.42; H, 7.35%.
δ 6.92 (1H, d, J = 16.3 Hz, CH CH), 7.20 (1H, s,
ArH), 7.20 (1H, d, J = 4.8 Hz, ArH), 7.24 (1H, d,
J = 4.8 Hz, ArH), 7.24 (1H, d, J = 16.3 Hz, CH CH),
7.33–7.36 (3H, m, ArH), 7.47 (2H, d, J = 7.0 Hz,
ArH); 13C NMR (126 MHz, CDCl3) δ 118.5, 119.7,
122.6, 126.4, 127.4, 127.8, 128.4, 128.8, 136.8, 138.0,
139.5, 145.2; IR (KBr) 3082, 1444, 947, 813, 690, 554
cm−1; EI-MS (70 eV) m/z 242 (M+); Anal. Calcd For
C14H10S2: C, 69.38; H, 4.16. Found: C, 69.22; H, 4.20
[32].
5,5ꢁ-Distyryl-2,2ꢁ-bithieno[3,2-b]thiophene (DS2TTs,
R = H). To a solution of compound 6a (0.853 g,
2-[p-(Butylphenyl)vinyl]-thieno[3,2-b]thiophene
n
3.52 mmol) in dry THF (30 mL) at 0◦C, BuLi (1.57
(6b). Yield 90%, pale yellow plate-like crystals; mp
M, 2.5 mL, 1.1 equiv) was added dropwise under ni-
trogen, and then the suspension was stirred for 0.5 h
at 0◦C and for an additional 0.5 h at room temper-
ature. Subsequently, CuCl2 (0.625 g, 1.3 equiv) was
added to the reaction mixture and refluxed for 18 h.
After cooling to room temperature, the solution was
quenched with water and acidified with HCl aq. The
mixture was then filtered and washed with water and
CHCl3. The resulting solid was dissolved in hot 1,2-
dichlorobenzene to remove any unwanted compo-
nents. The precipitate was collected by filtration, and
the title compound was collected as orange crystals
(0.298 g, 0.617 mmol, 36%). Decomposition point
383◦C; IR (KBr) 3060, 2367, 1619, 1442, 1160, 947,
804 cm−1; EI-MS (70 eV) m/z 482 (M+); Anal. Calcd
For C28H18S4: C, 69.67; H, 3.76. Found: C, 69.54; H,
3.91.
1
151–152◦C; H NMR (500 MHz, CDCl3) δ 0.93 (3H,
t, J = 7.6 Hz, CH2CH2CH2CH3), 1.36 (2H, sext,
J = 7.6 Hz, CH2CH2CH2CH3), 1.60 (2H, quint,
J = 7.6 Hz, CH2CH2CH2CH3), 2.61 (2H, t, J =
7.6 Hz, CH2CH2CH2CH3), 6.90 (1H, d, J = 16.0 Hz,
CH CH), 7.16 (2H, d, J = 8.0 Hz, ArH), 7.18 (1H,
s, ArH), 7.20 (2H, d, J = 16.0 Hz, CH CH), 7.33
(1H, d, J = 5.0 Hz, ArH), 7.38 (2H, d, J = 8.0 Hz,
ArH); 13C NMR (126 MHz, CDCl3) δ 14.0, 22.4, 33.6,
35.5, 118.1, 120.0, 121.6, 126.3, 127.2, 128.4, 128.8,
134.2, 137.8, 139.5, 142.8, 145.5; IR (KBr) 3085,
2927, 1459, 944, 828, 697, 560 cm−1; EI-MS (70 eV)
m/z 298 (M+); Anal. Calcd For C18H18S2: C, 72.43;
H, 6.08. Found: C, 72.38; H, 5.99.
2-[p-(Hexylphenyl)vinyl]-thieno[3,2-b]thiophene
(6c). Yield 93%, pale yellow plate-like crystals;
5,5ꢁ-Bis[p-(butylphenyl)vinyl]-2,2ꢁ-bithieno[3,2-
b]thiophene (DS2TTs, R = Bu): Yield 32%, orange
crystals; decomposition point 371◦C; IR (KBr) 2924,
2372, 1510, 1445, 947, 823, 554 cm−1; EI-MS (70 eV)
m/z 594 (M+); Anal. Calcd For C36H34S4: C, 72.68;
H, 5.76. Found: C, 72.69; H, 5.75.
◦
1
mp 143–144 C; H NMR (500 MHz, CDCl3) δ 0.88
(3H, t, J = 8.4 Hz, CH2CH2(CH2)3CH3), 1.27–1.37
(6H, m,
CH2CH2(CH2)3CH3), 1.59 (2H, quint,
J = 8.4 Hz, CH2CH2(CH2)3CH3), 2.60 (2H, t, J
= 8.4 Hz, CH2CH2(CH2)3CH3), 6.90 (1H, d, J =
16.3 Hz, CH CH), 7.16 (2H, d, J = 8.3 Hz, ArH),
7.18 (1H, s, ArH), 7.20 (1H, d, J = 5.0 Hz, ArH),
7.20 (1H, d, J = 16.3 Hz, CH CH), 7.34 (1H, d, J
= 5.0 Hz, ArH), 7.39 (2H, d, J = 8.3 Hz, ArH); 13C
NMR (126 MHz, CDCl3) δ 14.1, 22.6, 29.0, 31.3,
31.7, 35.8, 118.1, 119.7, 121.6, 126.3, 127.2, 128.5,
128.8, 134.2, 137.8, 139.5, 142.9, 145.6; IR (KBr)
3081, 2957, 1459, 945, 828, 698, 555 cm−1; EI-MS
(70 eV) m/z 326 (M+); Anal. Calcd For C20H22S2: C,
73.57; H, 6.79. Found: C, 73.41; H, 6.72.
5,5ꢁ-Bis[p-(hexylphenyl)vinyl]-2,2ꢁ-bithieno[3,2-
b]thiophene (DS2TTs, R = Hexyl): Yield 44%, orange
crystals; decomposition point 335◦C; IR (KBr) 3078,
2921, 2367, 1617, 1451, 1255, 1120, 946, 823, 554
cm−1; EI-MS (70 eV) m/z 650 (M+); Anal. Calcd for
C40H42S4: C, 73.80; H, 6.50. Found: C, 73.52; H,
6.44.
5,5ꢁ-Bis[p-(octylphenyl)vinyl]-2,2ꢁ -bithieno[3,2-
b]thiophene (DS2TTs, R = Octyl): Yield 34%, orange
crystals; decomposition point 315◦C; IR (KBr)
3078, 2920, 2370, 1617, 1451, 1255, 1120, 946, 823,
554 cm−1; EI-MS (70 eV) m/z 706 (M+); Anal. Calcd
for C44H50S4: C, 74.73; H, 7.13. Found: C, 74.70; H,
7.06.
2-[p-(Octylphenyl)vinyl]-thieno[3,2-b]thiophene
(6d). Yield 94%, pale yellow plate-like crystals;
1
mp 143–144◦C; H NMR (500 MHz, CDCl3) δ 0.88
(3H, t, J = 7.3 Hz, CH2CH2(CH2)5CH3), 1.26–1.31
(10H, m, CH2CH2(CH2)5CH3), 1.69 (2H, quint,
J = 7.3 Hz, CH2CH2(CH2)5CH3), 2.60 (2H, t, J
= 7.3 Hz, CH2CH2(CH2)5CH3), 6.90 (1H, d, J =
4-Butylbenzyltriphenylphosphinium
To a solution of triphenylphosphine (2.99 g, 11.4
mmol) in dry toluene (30 mL) at room temperature,
Bromide.
Heteroatom Chemistry DOI 10.1002/hc