A1 Refereed original research article in a scientific journal
Electrochemical polymerization of the tetrathienyl derivatives of the carbon group elements
Authors: Visy C, Lukkari J, Kankare J
Publisher: ELSEVIER SCIENCE SA LAUSANNE
Publication year: 1996
Journal:Journal of Electroanalytical Chemistry and Interfacial Electrochemistry
Journal name in sourceJOURNAL OF ELECTROANALYTICAL CHEMISTRY
Journal acronym: J ELECTROANAL CHEM
Volume: 401
Issue: 1-2
First page : 119
Last page: 125
Number of pages: 7
ISSN: 0022-0728
DOI: https://doi.org/10.1016/0022-0728(95)04261-X
Abstract
The electropolymerization of four tetrathienyl compounds of the carbon group elements (T(4)M, where M = Si, Ge, Sn or Pb) was studied on indium tin oxide electrodes in three organic solvents with low water content (acetonitrile, propylene carbonate and nitrobenzene). Only poorly conducting deposits were obtained in acetonitrile, but polymerization in propylene carbonate yielded partially electroactive films. The best polymers were formed in nitrobenzene, but none of the tetrathienyls tested produced polythiophene films superior to those prepared using thiophene as the monomer with the same experimental conditions. The polymerization mechanism of the thienylmetals is different from that of purely organic thiophene derivatives, as the oxidation produces neutral thiophene radicals in the former case, instead of radical cations. The results suggest that the reactive neutral thiophene radical can abstract a hydrogen atom from solvents such as acetonitrile, explaining the apparent contradiction in the polymerization efficiency of tetrathienyls and thiophene in this solvent.
The electropolymerization of four tetrathienyl compounds of the carbon group elements (T(4)M, where M = Si, Ge, Sn or Pb) was studied on indium tin oxide electrodes in three organic solvents with low water content (acetonitrile, propylene carbonate and nitrobenzene). Only poorly conducting deposits were obtained in acetonitrile, but polymerization in propylene carbonate yielded partially electroactive films. The best polymers were formed in nitrobenzene, but none of the tetrathienyls tested produced polythiophene films superior to those prepared using thiophene as the monomer with the same experimental conditions. The polymerization mechanism of the thienylmetals is different from that of purely organic thiophene derivatives, as the oxidation produces neutral thiophene radicals in the former case, instead of radical cations. The results suggest that the reactive neutral thiophene radical can abstract a hydrogen atom from solvents such as acetonitrile, explaining the apparent contradiction in the polymerization efficiency of tetrathienyls and thiophene in this solvent.
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