Electrochemical synthesis and optical analysis of poly[(2,2′‐dithienyl)‐5,5′‐diylvinylene]

The electrochemical synthesis of poly[(2,2′‐dithienyl)‐5,5′‐diylvinylene tetrafluoroborate] (PDTE/BF 4 ) has been accomplished and provides coppery‐black free‐standing films with a room‐temperature four‐probe conductivity as high as 15 (Ω cm) −1 . The conductivity and morphology of the films were found to be strongly dependent on synthetic conditions. The oxidized form of PDTE is not air stable, as evidenced by a rapid, three order of magnitude drop in the conductivity. Optoelectrochemical experiments demonstrate that bipolarons are the main charge‐carrying species in conductive PDTE and allow their evolution to be followed as a function of oxidation.