Synthesis and properties of end-capped bis(oligothienyl) sulfides

Abstract

The synthesis, and the optical and electrochemical properties, of a series of mesitylthio (MesS-) end-capped bis(oligothienyl) sulfides are presented. The target compounds were synthesized principally by convergent protocols, whereby a series of short thiophene oligomers bearing one terminal mesitylthio (MesS-) substituent were first assembled by metal-catalyzed cross-coupling reactions and then coupled via divalent sulfur through reactions with bis(phenylsulfonyl) sulfide. The spectroscopic and electrochemical features of the bis(oligothienyl) sulfides are qualitatively similar to those of the related mesitylthio-capped fully conjugated oligothiophenes, suggesting that the degree of electronic communication between the two oligothiophene chromophores in the bis(oligothienyl) sulfides is low. Cyclic voltammetry studies on the bis(oligothienyl) sulfides reveal that these species can be reversibly oxidized to radical cations, but the reversibility of subsequent oxidations depends on oligothienyl chain length and the presence and position of more electron-rich ethylenedioxythiophene (EDOT) groups. In general, the bis(oligothienyl) sulfides possess fewer than the expected number of reversible oxidations based on comparisons with their corresponding mesitylthio-capped fully conjugated oligothiophenes; excessive charge accumulation at or near the central linking sulfur atom is believed to be responsible for the irreversible behavior. Analysis of the irreversible voltammetric response of one of the bis(oligothienyl) sulfides leads to the suggestion of a decomposition mechanism for the cationic species involving carbon-sulfur bond cleavage and subsequent coupling of thiophene fragments — a finding with potential implications for the poor environmental stability of doped poly(p-phenylene sulfide), one of the prototypical conducting polymers.Key words: conjugated materials, conducting polymers, oligothiophenes, electronic communication.