Electronic structure of two-dimensional porphyrin polymers

The electronic structure of the acetylenyl-linked two-dimensional (2D) porphyrin polymer was studied with the use of the tight-binding crystal orbital (TBCO) method based on the extended Hückel approximation. Effects of the different bridging modes (bridging site and linking species) were also examined. It has been shown that meso-to-meso-bridged pophyrin polymerin linked with acetylenyl groups has the largest π-conjugation among the present polymer models. Moreover, analysis of the electronic properties has suggested that n-type doping will be promising toward electrically conductive 2D polymers.