Abstract
Abstract : Polymers of 3-ethylmercapto and 3,4-bis(ethylmercapto)thiophenes have been synthesized and characterized. These polymers are soluble in common organic solvents such as methylene chloride, chloroform and THF. Structural characterization using FT-IR and NMR spectroscopy show that these polymers have a well-defined beta-ethylmercapto substituted 2,5-(thienylene) polymeric structure. Visible-near IR absorption spectra of electrochemically doped cast films and chemically doped solutions of the polymers show that they can be oxidized to form bipolaronic species. GPC studies show a number average molecular weight of about 2500 (M w/M n approx. 5) for both polymers. Maximum electrical conductivities of 10-3/ohm/cm for the 3-ethylmercapto, and 10 to the -7th for the 3,4-bis(ethylmercapto)substituted polymers have been obtained in the oxidized state. Experimental results are correlated with theoretical calculations using the PRDDO and extended Huckel methods, which demonstrate radical-cation reactivities for the thiophene monomers, along with minimum energy conformations and band structures in these substituted polymers. Keywords: Conductive polymers; Substituted polythiophenes; Theoretical calculations; Thiophenes.
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