Metallomacrocycle (MacM) complex with cyanide as bridged ligand: Electronic structures of [MacMCN](n)

Abstract

The electronic structures of complexes and one-dimensional metallomacrocycles with cyanide as bridged ligand, such as [MacM(CN)(2)](-) and [MacM(CN)](n) [Mac = phthalocyanine, tetrabenzoporphyrine; M = Co(III), Rh(III)] have been investigated using density functional theory. The results of this study show that the intrinsic semiconductivity properties depend on the frontier bands. The valence band is composed by the pi-macrocycle orbital. The conduction band for the cobalt polymers is a mixture of orbitals between this metal and the cyanide ligand along of the stacking direction. However, in the rhodium polymers such a band is exclusively composed of the pi* system of the macrocycles.