Voltammetric characterization of soluble polyacetylene derivatives obtained from the ring-opening metathesis polymerization (ROMP) of substituted cyclooctatetraenes

Thomas H. Jozefiak, Eric J. Ginsburg, Christopher B. Gorman, Robert H. Grubbs, Nathan S Lewis

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Abstract

High molecular weight, amorphous, partially substituted polyacetylenes (poly-RCOT) have been prepared using the ring-opening metathesis polymerization of substituted cyclooctatetraenes. Spin-cast films of these polymers yielded unusually sharp, well-denned, reversible electrochemistry for oxidative and reductive doping processes. As the substituent on the polymer chain was varied (R = alkyl, tert-butoxy, trimethylsilyl, and p-X-phenyl), the potentials for oxidative and reductive doping changed by 0.3 V. In addition, the separation between the oxidative and reductive doping processes varied from 1.66 V to >2.0 V. Coulometry suggested that the reversible doping step represented a transfer of 1 electron for every 13-15 double bonds of the polymer. In contrast, the electrochemistry of predominantlycis poly-RCOT films was irreversible, and indicated the presence of an electrochemical cis-trans isomerization on the first voltammetric sweep through either reductive or oxidative doping. Spectroelectrochemical studies indicated that the electrochemically doped poly-RCOT materials (R = sec-butyl, (CH3)3Si) possessed mid-gap transitions at energies of 0.8-0.9 eV. The redox chemistry of the soluble, poly-RCOT (R = sec-butyl, (CH3)3Si) species in CH2Cl2 solution was also investigated. Voltammetric studies showed that both the reductive and oxidative doping processes were chemically irreversible, and indicated that the dissolved polymers were electroactive over a wide range of potentials.

Original languageEnglish
Pages (from-to)4705-4713
Number of pages9
JournalJournal of the American Chemical Society
Volume115
Issue number11
Publication statusPublished - 1993

ASJC Scopus subject areas

  • Chemistry(all)

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