TY - JOUR
T1 - Voltammetric Characterization of Soluble Polyacetylene Derivatives Obtained from the Ring-Opening Metathesis Polymerization (ROMP) of Substituted Cyclooctatetraenes
AU - Jozefiak, Thomas H.
AU - Ginsburg, Eric J.
AU - Gorman, Christopher B.
AU - Grubbs, Robert H.
AU - Lewis, Nathan S.
PY - 1993/6/1
Y1 - 1993/6/1
N2 - 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-defined, 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 predominantly-cis 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.
AB - 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-defined, 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 predominantly-cis 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.
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U2 - 10.1021/ja00064a035
DO - 10.1021/ja00064a035
M3 - Article
AN - SCOPUS:0001744098
VL - 115
SP - 4705
EP - 4713
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 11
ER -