THIOPHENE OLIGOMERS AS POLYTHIOPHENE MODELS .2. ELECTROCHEMISTRY AND INSITU ESR OF END-CAPPED OLIGOTHIENYLS IN THE SOLID-STATE - EVIDENCE FOR PI-DIMERIZATION OF HEXAMERIC POLARONS IN POLYTHIOPHENE

被引:128
作者
ZOTTI, G
SCHIAVON, G
BERLIN, A
PAGANI, G
机构
[1] UNIV MILAN,DIPARTIMENTO CHIM ORGAN & IND,I-20133 MILAN,ITALY
[2] CNR,CTR SPECIALI SINTESI ORGAN,I-20133 MILAN,ITALY
关键词
D O I
10.1021/cm00029a008
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
Thin films of thiophene oligomers (n = 4, 6, 8, and 10) methyl-protected toward anodic coupling at the terminal alpha positions were investigated by cyclic voltammetry and in situ ESR in acetonitrile. Reversible oxidation goes from a single one-electron step (tetramer) to a single two-electron step (octamer and decamer) through two separate one-electron steps (hexamer). ESR indicates strong magnetic dimerization for the one-electron-oxidized hexamer. The close resemblance of the electrochemical and ESR behavior of the hexamer with that of polythiophene suggests that oxidation of the latter occurs via hexameric spin-dimerized polarons. The hexameric model is discussed taking account of the oligomeric nature of polythiophene.
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页码:620 / 624
页数:5
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