The anodic oxidation of α-tetrathiophene on Pt was studied in a 1.0 mM monomer solution in 0.1 M LiClO4 in 45:35:20 acetonitrile/ethanol/DMF. Three consecutive oxidation peaks were detected by cyclic voltammetry, along with a cathodic peak related to the reduction of electroactive polarons formed during the first anodic process. Uniform, adherent, insoluble and black polymer films were obtained by chronoamperometry at 1.000 V vs Ag|AgCl corresponding to the first oxidation-polymerization process. Stirring of monomer solution promotes the production of polymer, favoring the oxidation of polymer chains with the incorporation of more doping ClO4- ions and ion pairs of Li+ClO4- in their monomeric units. The conductivity of the polymer obtained under stirring was three orders of magnitude higher than that synthesized from a quiescent solution. The scanning electron microscopy images also showed much more uniform films under stirring. This behavior points to the existence of less crosslinking in the polymer and the production of longer linear chains when the solution is stirred. IR analysis of these materials confirmed the formation of crosslinked chains with predominance of β-β linkages. Short linear oligomers such as the dimer, trimer and tetramer were detected in all polymers by MALDI-TOF-MS, thus showing a radical polycondensation as initial electropolymerization mechanism. A larger proportion of linear oligomers is formed under solution stirring.
