1260 Oyaizu et al.
Macromolecules, Vol. 37, No. 4, 2004
2,6-Dim eth yl-8,9-d id ecyl-3,4,5-tr ith ia -8,9-d ith ion ia cy-
clop en ta [1,2-a ;4,3-a ′]d ip en ta len e Tr ifla te (D-Me2F T3). Ac-
cording to the procedure essentially identical with the prepa-
ration of D-Me2F T2, D-Me2F T3 was prepared from DSO-T3
(0.13 g, 0.20 mmol). The product was obtained as a pale brown
energetic aspects of the coupling process from the heat
of formation calculated for a unit cell in the polaron
state and that in the bipolaron state at the same doping
level. The propriety of this treatment is discussed in this
paper.
1
powder (0.17 g, 0.19 mmol). Yield: 95%. H NMR (DMSO-d6,
500 MHz, ppm): δ 7.72 (s, 2H), 4.24 (m, J ) 8.6 Hz, 4H), 3.17
(s, 6H), 1.68, 1.37, 1.27, 0.88 (m, 38H). 13C NMR (DMSO-d6,
125 MHz, ppm): δ 173.0, 156.5, 145.2, 144.8, 129.8, 123.2, 76.6,
43.9, 31.6-27.0, 25.7, 18.4, 14.3, 13.9. IR (KBr, cm-1): 1251,
786 (νC-F), 1150 (νSO3), 826 (δC-H). Anal. Calcd for
3. Ma ter ia ls a n d Mea su r em en ts
3.1. Ma ter ia ls. See the Supporting Information for the
preparative methods for 3-decylsulfanyl-5,5′-dimethyl-[2,2′]-
bithiophenyl (DS-T2), 3,4′-bis(decylsulfanyl)-5,5”-dimethyl-
[2,2′;5′,2”]terthiophene (DS-T3), poly(3-decylsulfanylthiophene)
(DS-P T), and poly[3-(1-methylheptylsulfanyl)thiophene] (MS-
P T). Poly(3-hexylthiophene) (H-P T) was prepared from 2-bro-
mo-3-hexylthiophene by the conventional Grignard coupling
method.46-48 All solvents were purified by distillation prior to
use. Tetrabutylammonium tetrafluoroborate [(TBA)BF4] was
obtained from Tokyo Kasei Co., and recrystallized twice from
benzene/ethyl acetate. All other regents were obtained from
Kanto Chemical Co. or Tokyo Kasei Co. and used without
further purification.
C
36H50F6O6S7: C, 47.14; H, 5.49. Found: C, 48.11; H, 5.72.
2,6-Dim eth yl-3,4,5,8,9-p en ta th ia cyclop en ta [1,2-a ;4,3-a ′]-
d ip en ta len e (Me2F T3). According to the procedure essentially
identical with the preparation of Me2F T2, Me2F T3 was
prepared from D-Me2F T3 (0.092 g, 0.10 mmol). The product
was obtained as a pale brown powder (0.033 g, 0.098 mmol).
Yield: 98%. 1H NMR (CD2Cl2, 500 MHz, ppm): δ 7.05 (s, 2H),
2.48 (s, 6H). Anal. Calcd for C14H8S5: C, 49.96; H, 2.40.
Found: C, 49.22; H, 2.97.
P oly[3-(d eca n e-1-su lfin yl)th iop h en e] (DSO-P T). To a
solution of DS-P T (0.12 g, 0.44 mmol unit) in CH2Cl2 (14 mL)
was slowly added an aqueous solution of hydrogen peroxide
(30%, 2.4 mL) and acetic acid (1 mL). After stirring at 30 °C
for 15 h, the resulting mixture was poured into methanol/water
(v/v ) 1/1) to precipitate the product which was collected by
filtration and dried under vacuum to give DSO-P T as a red
powder (0.11 g, 0.39 mmol unit). Yield: 89%. 1H NMR (CDCl3,
500 MHz, ppm): δ 7.69 (s, 1H), 3.10, 2.90 (m, 2H), 1.80, 1.68,
1.65, 1.45, 1.25, 0.92 (m, 19H). 13C NMR (CDCl3, 125 MHz,
ppm): δ 173.2, 142.4, 126.3, 126.1, 56.5, 31.9, 29.9, 29.8, 29.7,
29.5, 29.4, 28.9, 22.8, 14.3. GPC (THF, polystyrene standard):
Mn ) 6200, Mw ) 7500 (Mw/Mn ) 1.2). UV-vis (CHCl3, nm):
λmax ) 468 nm. IR (KBr, cm-1): 1058 (νSdO), 723 (δC-H). Anal.
Calcd for C14H22OS2: C, 62.17; H, 8.20. Found: C, 62.09; H,
8.01.
3-(Deca n e-1-su lfin yl)-5,5′-d im et h yl-[2,2′]b it h iop h en -
yl (DSO-T2). A mixture of DS-T2 (0.20 g, 0.57 mmol) in CH2-
Cl2 (40 mL), an aqueous solution of hydrogen peroxide (30%,
8 mL), and acetic acid (2 mL) was stirred at 30 °C for 3 h. The
organic layer was extracted with CHCl3, and the extract was
washed with water. Dehydration of the extract followed by
evaporation of the solvent gave the product as a yellow powder
1
(0.21 g, 0.52 mmol). Yield: 92%. H NMR (CDCl3, 500 MHz,
ppm): δ 7.19 (s, 1H), 6.86 (d, J ) 3.4 Hz, 1H), 6.58 (d, J ) 3.5
Hz, 1H), 2.97-2.74 (m, 2H), 2.46 (s, 3H), 2.40 (s, 3H), 1.58,
1.33, 1.18, 0.87 (m, 19H). 13C NMR (CDCl3, 125 MHz, ppm):
δ 140.0, 139.6, 138.6, 137.0, 133.7, 125.9, 124.1, 118.5, 55.7,
31.8, 29.4, 29.3, 29.2, 29.1, 28.9, 28.7, 23.7, 22.6, 15.3, 14.1.
MS (EI, m/z): calcd for M+ 382.66; found 382. IR (KBr, cm-1):
1052 (νSdO), 834 (δC-H). Anal. Calcd for C20H30OS3: C, 62.78;
H, 7.90. Found: C, 63.25; H, 8.59.
4-Decyl-2,6-d im eth yld ith ien o[3,2-b;2′,3′-d ]th iop h en -4-
iu m Tr ifla te (D-Me2F T2). DSO-T2 was dissolved in triflic acid
(16 mL), and the resulting solution was stirred at 80 °C for 24
h. After cooling, the solution was poured into diethyl ether (500
mL) to precipitate the product which was collected by filtration,
washed with diethyl ether, and dried under vacuum to give a
P oly[3-(1-m eth ylh ep ta n e-1-su lfin yl)th iop h en e] (MSO-
P T). According to the procedure essentially identical with the
preparation of DSO-P T, MSO-P T was prepared from MS-P T
(0.030 g, 0.13 mmol unit). The product was obtained as a dark
red powder (0.027 g, 0.11 mmol unit). Yield: 81%. 1H NMR
(CDCl3, 500 MHz, ppm): δ 7.66 (s, 1H), 3.22, 2.93 (m, 1H),
1.80, 1.48, 1.28, 0.89 (m, 16H). 13C NMR (CDCl3, 125 MHz,
ppm): δ 165.2, 143.0, 127.6, 126.5, 59.6, 37.9, 31.9, 29.5, 27.7,
26.4, 22.4, 14.4. GPC (THF, polystyrene standard): Mn ) 5400,
Mw ) 7600 (Mw/Mn ) 1.4). UV-vis (CHCl3, nm): λmax ) 454
nm. IR (KBr, cm-1): 1052 (νSdO), 722 (δC-H). Anal. Calcd for
1
pale brown powder (0.39 g, 0.76 mmol). Yield: 95%. H NMR
(DMSO-d6, 500 MHz, ppm): δ 7.66 (s, 2H), 4.15 (t, J ) 7.2
Hz, 2H), 2.76 (s, 6H), 1.64, 1.38, 1.27, 0.88 (m, 19H). 13C NMR
(DMSO-d6, 125 MHz, ppm): δ 166.7, 131.6, 131.2, 128.4, 67.3,
38.1, 29.7, 29.5, 29.5, 29.3, 29.1, 28.6, 22.7, 15.3, 14.1. IR (KBr,
cm-1): 1259, 794 (νC-F), 1157 (νSO3), 839 (δC-H). Anal. Calcd
for C21H29F3O3S4: C, 49.00; H, 5.68. Found: C, 48.23; H, 6.32.
2,6-Dim eth yld ith ien o[3,2-b;2′,3′-d ]th iop h en e (Me2F T2).
D-Me2F T2 (0.21 g, 0.4 mmol) was dissolved in pyridine (15
mL), and the resulting solution was refluxed for 24 h with
constant stirring. After cooling, the solution was poured into
hydrochloric acid (200 mL). The pale brown precipitate was
collected by filtration, washed with water, and dried under
vacuum to give the product (0.09 g, 0.39 mmol). Yield: 97%.
1H NMR (CD2Cl2, 500 MHz, ppm): δ 7.01 (s, 2H), 2.48 (s, 6H).
MS (EI, m/z): calcd for M+ 224.37; found 224. IR (KBr, cm-1):
845 (δC-H). Anal. Calcd for C10H8S3: C, 53.05; H, 3.56. Found:
C, 53.10; H, 3.87.
C
12H18OS2: C, 59.46; H, 7.49. Found: C, 58.97; H, 7.31.
Th e Rin g-Closed P r od u ct fr om DSO-P T (D-LP T). A
solution of DSO-P T (0.095 g, 0.50 mmol unit) in CH2Cl2 (2
mL) was added dropwise to triflic acid (20 mL) with constant
stirring. The solution was warmed to 60 °C and stirred for 1
h to remove CH2Cl2. The resulting solution of DSO-P T in triflic
acid was stirred at 80 °C for 24 h to undergo the ring-closing
reaction. The reaction was quenched by pouring the mixture
into diethyl ether (300 mL) to precipitate the product. The
precipitate was collected by filtration and dried under vacuum
to give D-LP T as a dark brown powder (0.20 g). Yield: 96%.
1H NMR (DMSO-d6, 500 MHz, ppm): δ 3.64 (m, 2H), 1.37, 0.88
(m, 19H). IR (KBr, cm-1): 1153, 1356 (νSO3), 753 (δC-H), 636
(νC-F). UV-vis (CHCl3, nm): λmax ) 569 nm. Anal. Calcd for
3,4′-Bis(d eca n e-1-su lfin yl)-5,5”-d im eth yl-[2,2′;5′,2”]ter -
th iop h en e (DSO-T3). According to the procedure essentially
identical with the preparation of DSO-T2, DSO-T3 was
prepared from DS-T3 (0.31 g, 0.50 mmol) by the oxidation of
the decylsulfanyl group at 30 °C for 8 h. The product was
obtained as a yellow powder (0.30 g, 0.46 mmol). Yield: 95%.
1H NMR (CDCl3, 500 MHz, ppm): δ 7.46 (s, 1H), 7.34 (s, 1H),
7.02 (d, J ) 3.5 Hz, 1H), 6.69 (d, J ) 3.5 Hz, 1H), 2.99 (m, J
) 8.8 Hz, 4H), 2.59 (s, 3H), 2.50 (s, 3H), 1.74, 1.43, 1.25, 0.87
(m, 38H). 13C NMR (CDCl3, 125 MHz, ppm): δ 140.0, 139.6,
138.6, 137.0, 133.7, 125.9, 124.1, 118.5, 55.7, 31.8, 29.4-28.7,
23.7, 22.6, 15.3, 14.1. MS (EI, m/z): calcd for M+ 653.11; found
653. IR (KBr, cm-1): 1050 (νSdO), 828 (δC-H). Anal. Calcd for
C
15H21F3O3S3: C, 44.76; H, 5.26. Found: C, 44.02; H, 5.11.
Th e Rin g-Closed P r od u ct fr om MSO-P T (M-LP T).
According to the procedure essentially identical with the
preparation of D-LP T, M-LP T was prepared from MSO-P T
(0.025 g, 0.11 mmol unit). The product was obtained as a dark
red powder (0.036 g, 0.10 mmol unit). Yield: 90%. 1H NMR
(DMSO-d6, 500 MHz, ppm): δ 3.50 (m, 1H), 2.10, 1.72, 1.20,
0.93 (m, 16H). IR (KBr, cm-1): 1169, 1389 (νSO3), 714 (δC-H),
646 (νC-F). UV-vis (CHCl3, nm): λmax ) 536 nm. Anal. Calcd
for C13H17F3O3S3: C, 41.70; H, 4.58. Found: C, 40.99; H, 4.32.
La d d er -Typ e P olyt h iop h en e (LP T). The ring-closed
polymer, M-LP T, was converted to LP T by treatment with
pyridine as follows. A suspension of M-LP T (0.035 g, 0.093
mmol unit) in pyridine (15 mL) was refluxed for 24 h. After
C
34H52O2S5: C, 62.53; H, 8.03. Found: C, 62.01; H, 8.98.