3J=8.06 Hz, 2 Ar-H), 8.20 (s, 4H, 2 B-(OH) ), 7.93 (d, 2H,
3J=8.06 Hz, 2 Ar-H).
(100 ml). The yellow precipitate was collected by suction
filtration and washed with a large amount of methanol. The
structure of this compound, which was insoluble in ordinary
organic solvents, was assumed to be 18. Demethylation of the
solid was achieved by refluxing in pyridine (20 ml) for 12 h.
When the suspension was cooled to room temperature, a large
volume of acetone was added. DBTBT 1 was thus obtained
by suction filtration and crystallisation from boiling quinoline
as pale yellow plates (210 mg, 86% related to 8). mp: 299.6 °C
(determined by differential scanning calorimetry (DSC)). FD-
2
2-Bromo(methylsulfinyl)benzene (16). 2-Bromothioanisole
(15) (3.3 g, 16.25 mmol) was dissolved in glacial acetic acid
and cooled with an ice-bath till the solvent was about to
freeze. Hydrogen peroxide (35%, 1.81 g) was added slowly.
The cooling bath was removed and the mixture was stirred at
room temperature for 12 h. Acetic acid was removed by
vacuum evaporation and water (50 ml) was added to the
residue. The precipitated oil was taken up with dichloro-
MS: m/z=396.0 (100%) [M+]. Anal. Calc. for C H S : C
24 12 3
72.69, H 3.05; found: C 72.63, H 3.19%.
methane, the solution washed with saturated NaHCO solution
3
and dried over MgSO . Evaporation of the solvent yielded
4
3.5 g (98%) of 16 as a viscous colorless oil. 1H-NMR
Acknowledgements
(200 MHz, CDCl ): d=7.96 (m, 1H, 1 Ar-H), 7.59 (m, 2H, 2
3
Financial support from the British Royal Society (URF) and
the Engineering and Physical Sciences Research Council is
gratefully acknowledged. JL thanks the Fonds der Chemischen
Industrie for a stipend.
Ar-H), 7.38 (m, 1H, 2 Ar-H), 2.82 (s,3H, S-CH ). 13C-NMR
3
(50 MHz, CDCl ): d=145.25, 132.63, 131.98, 128.43, 125.38,
3
117.81, 41.69. FD-MS (8 kV): m/z=218.9 (100%) [M+].
3,7-Bis[2-(methylsulfinyl)phenyl])dibenzothiophene (8). To the
stirred solution of sulfoxide 16 (2.63 g, 12 mmol) in freshly
References
distilled THF (150 ml), Pd(PPh ) (416 mg, 0.36 mmol) was
3 4
1
C. J. Drury, C. M. J. Mutsaers, C. M. Hart, M. Matters and D. M.
de Leeuw, Appl. Phys. Lett., 1998, 73, 108.
added in one portion under argon. The mixture was stirred for
10 min, then diboronic acid 13 (1.36 g, 5 mmol) and 2 M
2
H. Sirringhaus, N. Tessler and R. H. Friend, Science, 1998, 280,
Na CO solution (15 ml) were added. The flask was covered
1741.
2
3
with aluminium foil and the mixture was heated to reflux and
stirred vigorously for 20 h. THF was evaporated followed by
decantation of the upper water phase to obtain a greenish–
yellow oily residue. The soluble part of the residue was chromato-
graphed (silica gel, EtOAc–MeOH (951)) to get a white solid of
8 (1.81 g, 51%). From a second fraction 0.25 g of byproduct 17
were isolated as a white solid. The formation of the latter
compound 17 is described in Scheme 5. Mp of both compounds
3
4
H. E. Katz, J. Mater. Chem., 1997, 7, 369.
F. Garnier, R. Hajlaoui, A. Yassar and P. Srivastava, Science,
1994, 265, 1684.
5
6
7
8
9
J. G. Laquindanum, H. E. Katz and A. J. Lovinger, J. Am. Chem.
Soc., 1998, 120, 664.
H. E. Katz, A. J. Lovinger and J. G. Laquindanum, Chem. Mater.,
1998, 10, 457.
Y. Y. Lin, D. J. Gundlach, S. F. Nelson and T. N. Jackson, IEEE
Trans. Electron. Devices, 1997, 44, 1325.
J. G. Laquindanum, H. E. Katz, A. J. Lovinger and
A. Dodabalapur, Adv. Mater., 1997, 9, 36.
>300°C. Spectral data of 8: 1H-NMR (250 MHz, CDCl ): d=
3
8.24 (d, 2H, 3J=6.52 Hz, 2 Ar-H), 8.15 (dd, 2H, 3J=6.54 Hz,
H. Sirringhaus, R. H. Friend, X. C. Li, S. C. Moratti, A.
B. Holmes and N. Feeder, Appl. Phys. Lett., 1997, 71, 3871.
4J=1.26 Hz, 2 Ar-H), 7.88 (d, 2H, 4J=1.26 Hz, 2 Ar-H), 7.65
(dt, 2H, 3J=6.54 Hz, 4J=1.26 Hz, 2 Ar-H), 7.57 (dt, 2H, 3J=
6.54 Hz, 4J=1.26 Hz, 2 Ar-H), 7.50 (dd, 2H, 3J=6.54 Hz, 4J=
10 K. Yamamoto, E. Shouji, H. Nishide and E. Tsuchida, J. Am.
Chem. Soc., 1993, 115, 5819.
11 E. Tsuchida, E. Shouji and K. Yamamoto, Macromolecules, 1993,
26, 7144.
12 L. Wang, T. Soczka-Guth, E. Havinga and K. Mullen, Angew.
Chem., Int. Ed. Engl., 1996, 35, 1495.
13 J. Leuninger, C. Wang, T. Soczka-Guth, V. Enkelmann, T. Pakula
and K. Mullen, Macromolecules, 1998, 31, 7120.
14 J. Leuninger, J. Uebe, J. Salbeck, L. Gherghel, C. Wang and
1.26 Hz, 2 Ar-H), 2.36 (s, 6H, SO-CH ). 13C-NMR (62.5 MHz,
3
CDCl ): d=144.00, 140.33, 138.78, 136.83, 134.75, 130.82,
3
¨
130.51, 129.09, 125.89, 123.53, 123.32, 122.02, 41.70. FD-MS
(8 kV): m/z=460.5 (100%) [M+].
4H, 3J=5.78 Hz, 4 Ar-H), 8.15 (dd, 4H, 3J=5.78 Hz, 4J=
Spectral data of 17: 1H-NMR (250 MHz, CDCl ): d=8.24 (t,
3
¨
1.26 Hz, 4 Ar-H), 7.86 (d, 2H, 4J=1.26 Hz, 2 Ar-H), 7.80 (dd,
2H, 3J=5.78 Hz, 4J=1.26 Hz, 2 Ar-H), 7.65 (dt, 2H, 3J=
5.78 Hz, 4J=1.26 Hz, 2 Ar-H), 7.56 (dt, 2H, 3J=5.78 Hz, 4J=
1.26 Hz, 2 Ar-H), 7.47 (dd, 2H, 3J=5.78 Hz, 4J=1.26 Hz, 2 Ar-
H), 7.39 (dd, 2H, 3J=5.78 Hz, 4J=1.26 Hz, 2 Ar-H) 2.37 (s,
6H, SO-CH ). 13C-NMR (62.5 MHz, CDCl ): d=143.93,
140.64, 140.30, 139.75, 138.92, 136.42, 135.03, 134.21, 130.80,
130.53, 129.01, 125.72, 124.32, 123.51, 123.26, 122.14, 121.86,
121.39, 41.68. FD-MS (8 kV): m/z=642.1 (100%) [M+].
K. Mullen, Synth. Met., 1999, in the press.
15 R. M. Acheson and J. K. Stubbs, J. Chem. Soc., Perkin Trans. 1,
1972, 1, 899.
16 N. M. Cullinane and C. G. Davies, J. Chem. Soc., 1936, 1435.
17 W. Gottardi, Monatsh. Chem., 1968, 98, 507.
¨
18 R. Gerdil and E. A. C. Lucken, J. Am. Chem. Soc., 1965, 87, 213.
19 N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, 2457.
20 S. E. Wiberly and R. D. Gonzalez, Appl. Spectrosc., 1961, 15, 174.
3
3
21 J. Leuninger, PhD Thesis, Johannes Gutenberg-Universitat,
¨
Mainz (1999).
22 M. S. Shur, M. Hack and J. G. Shaw, J. Appl. Phys., 1989, 66,
3371.
Dibenzo[b,b∞]thieno[2,3-f55,4-f∞]bis[1]benzothiophene
23 J. H. Schon, C. Kloc, R. A. Laudise and B. Batlogg, Phys. Rev. B,
¨
(DBTBT, 1). A 10 ml round bottomed flask was filled with 3,7-
bis[2-(methylsulfinyl)phenyl]dibenzothiophene (8) (270 mg,
0.59 mmol) and trifluoromethanesulfonic acid (3 ml). The
mixture was stirred for 12 h at room temperature to give a
dark green solution, which was then poured into ice–water
1998, 58, 12952.
24 J. Grimme, M. Kreyenschmidt, F. Uckert, K. Mullen and
¨
U. Scherf, Adv. Mater., 1995, 7, 292.
Paper 9/02679G
J. Mater. Chem., 1999, 9, 2095–2101
2101