Polyanilines. On the interplay between chemical and electronic structure

Polyanilines constitute a family of polymers which have recently attracted much attention in the field of conducting polymers. In this contribution, we focus on the three main forms of polyaniline: (a) leucoemeraldine, the reduced form; (b) emeraldine, the semi-oxidized form; and (c) pernigraniline, the fully oxidized form. We illustrate how the modifications in chemical structure impact on the major electronic properties, such as the nature of the bandgap. We also discuss the influence of ring rotations and ring or nitrogen substitutions on the magnitude of the gap and on the mobility of charge carriers, such as polarons, which are created upon protonation.