Structure and stereochemistry of electrochemically synthesized poly-(1-naphthylamine) from neutral acetonitrile solution

Poly-(1-naphthylamine) films were synthesized potentiodinamically and potentiostatically from 1-naphthylamine in neutral acetonitrile medium using a platinum electrode. These polymer films were investigated by infrared spectroscopy. Contrary to earlier published results neglecting the stereochemistry of die poly-(1-naphthylamine), we predict on the basis of quantum stereochemical analysis of the possible structural subunits of the polymer, that the ordinary N-C(4) coupled product is riot predominant in the polymer because it is far removed from the expected planarity. Based on the results of IR investigations and semiempirical quantum chemical calculations, it is proposed that the polymer products are formed via mixed N-C(4). N-C(5) and N-C(7) coupling routes. The heats of formation of the oxidized 1-naphthylamine dimers and hexamers were calculated.