DFT and TDDFT study of Al(III), Ga(III), In(III) porphyrazinates and their perhalogenated derivatives

Abstract

The effect of perhalogenation (F, Cl) of porphyrazine macrocycle on the molecular structure, electronic and spectral properties of AlIII, GaIII, InIII complexes bearing axial pentafluorophenoxy (C6F5O) group was investigated by DFT and TDDFT methods. Interactions between the axial pentafluorophenoxy group and porphyrazine core were carried out using the Symmetry-Adapted Perturbation Theory (SAPT0) method. According to the calculation results, the nature of the metal atom and peripheral halogenation slightly affect the geometry parameters. Analysis of the simulated spectra showed a bathochromic shift of the Q-band for perchlorinated complexes which correlates with narrowing of the HOMO-LUMO gap.