| 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 π‐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 π* system of the macrocycles. © 2002 John Wiley & Sons, Inc. Int J Quantum Chem, 2002 |
