Static polarization of the supramolecular dyads of fullerene C60 with porphyrin derivatives

Abstract

The nonlinear optical properties of four supramolecular dyads consisting of fullerene C 60 non-covalently bonded to porphyrin, porphyrazine, tetrabenzoporphyrin and phthalocyanine were investigated by calculating their electronic polarizability and first- and second-order hyperpolarizabilities using the finite field method and the density functional theory with the Grimme dispersion correction. Large first- and second-order hyperpolarizabilities result in nonlinear dependence of the polarization of dyads on the strength of external electric field. The increase in the size of the π-conjugated electron system of the porphyrin analogs leads to the increase of the polarizability and first- and second-order hyperpolarizabilities of the dyads. The absence of the covalent bonds between the components of the dyads prevents the field-induced electron transfer from porphyrin analogs to fullerene. The main reason for the nonlinear behavior of the polarization of dyads is the mutual polarization of fullerene and porphyrin analogs amplified by the external electric field.