Abstract

Abstract : The electrooxidation of alpha,alpha-coupled thiophene oligomers with terminal trimethylsilyl and P-methyl groups was studied in methylene chloride at room temperature. The oligomers with 4, 5, and 7 thiophene rings undergo two stepwise oxidations to produce the radical cation and dication, respectively, as confirmed by Vis/Nir esr spectra. The redox wave are chemically reversible and are well-separated (ca. 200 mV) in the cyclic voltammagram and suggested that the same electrochemical behavior should be observed with the next higher oligomers or in the n-conjugated segments of polythiophene. Thus the broad featureless voltammagram observed with films of polythiophene is not an inherent property of the polymer segments but may reflect complications from the solid state nature of the film.

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