title: Long-chain 3,4-ethylenedioxythiophene/thiophene oligomers and semiconducting thin films prepared by their electropolymerization.
abstract: A series of soluble H-terminated conjugated oligomers incorporating 3,4-ethylenedioxythiophene (EDOT) combined with a small number of thiophene units and ranging in length from four to eight EDOT/thiophene groups was prepared with the ultimate goal to investigate if facile formation of a reactive trication radical species would enable electrochemical polymerization of such long-chain oligomers. Spectroscopic and electrochemical studies of the oligomers revealed some general dependencies of their electronic properties on the total number and position of EDOT groups. It was the number of consecutive EDOT units rather than total number of these units which was found to have the most profound effect on electronic energy gap and conjugation length. This influence originates from the especially strong planarization induced in the conjugated backbone by the incorporation of EDOT units. In contrast, incorporation of thiophene units was found to result in loss of the conformational stabilization. This phenomenon was analyzed using the natural bond orbital computational approach, which revealed the predominantly hyperconjugative nature of the EDOT-induced conformational stabilization. Whereas shorter oligomers, in agreement with the general consensus, were found to be inert toward electrochemical polymerization due to low reactivity of electrochemically generated cation radical and dication species, the longest oligomer showed an unprecedentedly efficient electropolymerization to yield a stable thin film of an electroactive polymer. The efficient electropolymerization of the long-chain oligomer was found to be in agreement with the formation of a reactive trication radical species. The electronic and spectral properties of the resulting semiconducting polymer film were studied by various electrochemical and spectroelectrochemical methods, as well as conductive probe AFM technique, and revealed a number of unusual features (such as electrical rectifying switching behavior) consistent with the possibility of increased molecular order in this material.
authors.affiliation: Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
authors.forename: K M Nalin
authors.initials: KM
authors.lastname: de Silva
authors.forename: Euiyong
authors.initials: E
authors.lastname: Hwang
authors.forename: Wilson K
authors.initials: WK
authors.lastname: Serem
authors.forename: Frank R
authors.initials: FR
authors.lastname: Fronczek
authors.forename: Jayne C
authors.initials: JC
authors.lastname: Garno
authors.forename: Evgueni E
authors.initials: EE
authors.lastname: Nesterov