Complexation of free-base and 3d transition metal(II) phthalocyanines with fullerene C60: A dispersion-corrected DFT study

Abstract

ABSTRACTWe performed a systematic comparative theoretical study of noncovalent interactions of free-base H2Pc and a series of 3d transition metal(II) phthalocyanines (where the transition metals included manganese, iron, cobalt, nickel, copper and zinc) with fullerene C60, by employing a DFT technique accounting for vdW interactions (PBE GGA functional with a dispersion correction by Grimme). We observed four different types of Pc interaction with fullerene cage, depending on central metal atom. Upon complexation with C60, the macrocyclic plane undergoes distortion in all cases, to a different degree. Some correlation was observed between the calculated formation energies for Pc–fullerene complexes and intermolecular separations in them, where stronger binding is generally associated with shorter M…CC60 and N…CC60 distances. Despite of considerable differences in the structure of Pc–fullerene complexes, the latter do not exhibit notable variations in the distribution of electrostatic potential, contrary to spin density plots for open-shell species. Similarly, HOMO and LUMO distribution can vary within some limits.