Preparation of conjugated gels of regioregular HT sexi(3-n-octylthiophene) and related star molecules

被引:26
作者
Bras, J
Guillerez, S
Pépin-Donat, B
机构
[1] Univ Grenoble 1, Lab Phys Met Synthet, UMR 5819,CEA Grenoble, CNRS,Dept Rech Fondamentale Mat Condensee, F-38054 Grenoble 9, France
[2] Univ Grenoble 1, Lab Electrochim Mol & Struct Interfaces, UMR 5819,CEA Grenoble, CNRS,Dept Rech Fondamentale Mat Condensee, F-38054 Grenoble 9, France
关键词
D O I
10.1021/cm9911971
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We present new kinds of conducting gels of octylthiophene. Contrary to the gels previously obtained in our laboratory, they present two "high" gelation thresholds (i.e., related to high crosslink ratios). Consequently, systems close to the gelation threshold can be prepared with accuracy. Furthermore, they are calibrated and regioregular: The length and the regioregularity of the chain segments between adjacent cross-links are fully controlled. They are prepared by chemical polycondensation of monodisperse regioregular [(head-to-tail (HT)] oligo(octylthiophene)s with tribromobenzene. For the preparation of these gels, two kinds of regioregular oligomers are synthesized: linear (from dimer to hexamer) and "star" oligo(octylthiophene)s. The two star oligomers are made of a benzene ring trisubstituted in meta positions by a regioregular (HT) segment of respectively six (E6) and twelve (E12) octylthiophenes. The structural properties of the oligomers are studied by H-1 and C-13 NMR spectroscopy; information concerning their conformation is reported. The optical properties (UV-vis absorption and fluorescence) of the star oligomers are compared with that of the linear oligomers. A linear evolution of the energy of the fluorescence transitions of the linear regioregular oligo(octylthiophene)s with the reverse of thiophene number is demonstrated for the first time. The Stille coupling chosen to prepare the gels from the oligomers is studied to determine the experimental conditions allowing both the good solubility of large clusters formed during the gel preparation and the good yield of the coupling reaction. A first series of 14 networks is reported. It is characterized by two gelation thresholds that are very high, as expected, but very close one from another. A strategy is proposed to increase the distance between the two gelation thresholds in the coming series.
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页码:2372 / 2384
页数:13
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