Bidimensional Spectroelectrochemistry Applied to the Electrosynthesis and Characterization of Conducting Polymers: Study of Poly[4,4′‐bis(butylthio)‐2,2′‐bithiophene]

Abstract The electropolymerization mechanism of 4,4′‐bis(butylthio)‐2,2′‐bithiophene ( 1 ) was studied by means of bidimensional spectroelectrochemistry. Simultaneous electrochemical and spectroscopic signals were analyzed with the aim of obtaining information about the role of the low‐molecular‐weight oligomers in the polymerization process. Experiments in electrochemical cells with finite (thin layer) and semi‐infinite diffusion geometries were carried out to elucidate the role the oligomeric species play, both in the nucleation step and in the subsequent growth of the polymer deposited onto the electrode surface.