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 language | English |
|---|---|
| Pages (from-to) | 4705-4713 |
| Number of pages | 9 |
| Journal | Journal of the American Chemical Society |
| Volume | 115 |
| Issue number | 11 |
| Publication status | Published - 1993 |
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Voltammetric characterization of soluble polyacetylene derivatives obtained from the ring-opening metathesis polymerization (ROMP) of substituted cyclooctatetraenes. / Jozefiak, Thomas H.; Ginsburg, Eric J.; Gorman, Christopher B.; Grubbs, Robert H.; Lewis, Nathan S.
In: Journal of the American Chemical Society, Vol. 115, No. 11, 1993, p. 4705-4713.Research output: Contribution to journal › Article
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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
Y1 - 1993
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-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.
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-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.
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M3 - Article
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 -