INFLUENCE OF ANNELATION ON THE ELECTRONIC-PROPERTIES OF PHTHALOCYANINE MACROCYCLES

Service de Chimie des Matériaux Nouveaux et Département des Matériaux et Procédés, Université de Mons, Avenue Maistriau, 21, B-7000 Mons, Belgium We present the results of valence effective Hamiltonian (VEH) nonempirical pseudopotential calculations on the electronic structure of various macrocycles including tetraazaporphyrin, phthalocyanine, 2,3-naphthalocyanine, 1,2-naphthalocyanine, and phenanthrenocyanine. We focus our attention on the evolution of the oxidation potentials and lowest optical absorptions as a function of linear or angular annelation of benzene rings onto the basic tetraazaporphyrin macrocycle. The VEH results are found to agree with cyclic voltammetry and optical absorption experimental data. These results provide a coherent picture of the evolution of the electrical conductivity properties in crystals and polymers derived from those compounds. © 1990, American Chemical Society. All rights reserved.