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 p-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. KEYWORDS: hyperpolarizabilities, dispersion interaction, finite field method, cumulative atomic multipole moments formalism. ◊ SPP full member in good standing *Correspondence to: Pavel O. Krasnov, email: kpo1980@ gmail.com, tel: +7 908-020-9830 J. Porphyrins Phthalocyanines 2015.19:838-844. Downloaded from www.worldscientific.com by EMORY UNIVERSITY on 07/30/15. For personal use only.

Efficient synthesis of metallated thioporphyrazines in task specific ionic liquids and their spectroscopic investigation of binding with selected transition metal ions

“…The Pd(II) complexes are suitable for investigating the self assembly processes in solution via titration experiments. 25 27 The formation of the exocyclic Pd(II) adducts of all porphyrazine macrocycles significantly alters the electronic spectra by diminishing n − π * transitions and a sharpening of the Q band 28 which is evident in the UV-Vis spectral studies of [2,3,7,8,12,13,17,18-Octakis(heptylthio)-5,10,15,20-porphyrazinato] zinc(II) (7c). The main possibility of the binding of Pd(II) ion to complex 7c will occur at the thio group.…”