Density functional study of the redox processes in subphthalocyanines

A theoretical investigation on the redox processes in the subphthalocyanines (SubPcs) was performed. Singly and doubly oxidative and reductive transformations were considered. The full geometry optimization of the participating molecules showed that the cone shape arrangement of the SubPc is preserved in their ionic derivatives even when two electrons are either donated or subtracted from the molecule. The biggest geometric changes under electron exchange processes were calculated for the BCl bond distance. The electronic density distribution over all the products remains almost invariable with respect to the neutral molecule. Our calculations on the neutral and charged SubPcs demonstrated that they behave as conjugated systems, their electronic parameters being correlatively altered by the redox electron exchange. Further, the electronic state of the macrocycle atoms also depends on an intense electronic flow among the macrocyclic skeleton and the surrounding (axial chlorine and peripheral hydrogen) atoms that is associated with the redox process. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003