Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials

In this research, we investigated the second-order nonlinear optical (NLO) properties of multicomponent hybrid materials formed by meso-tetraphenylporphyrin P (both as free base and Zn-II complex), carrying in 2 or 2,12 beta-pyrrolic position an electron donor ferrocene (Fc), and/or an electron acceptor fullerene (C60) moiety, connected to the porphyrin core via an ethynyl or an ethynylphenyl spacer. We measured the NLO response by the electric-field-induced second-harmonic generation (EFISH) technique in CH2Cl2 solution with a 1907 nm incident wavelength, recording for all the investigated compounds unexpected negative values of mu beta(1907). Since density functional theory (DFT) calculations evidenced for P-Fc dyads almost null ground state dipole moments and very low values for P-C60 dyads and Fc-P-C60 triads, our EFISH results suggested a significant contribution to gamma(EFISH) of the purely electronic cubic term gamma(-2 omega; omega, omega, 0), which prevails on the quadratic dipolar orientational one mu beta(-2 omega; omega, omega)/5kT, as confirmed by computational evidence.