Study of geometric, electronic structures and vibrations of 4, 4′, 4′′, 4′′′-(porphine-5,10,15,20 tetrayl) tetrakis (benzene sulfonic acid) compound by computational and experimental techniques

Abstract

The optimized geometry and vibrational frequencies of a substituted compound of tetraphenylporphine namely 4, 4[Formula: see text], 4[Formula: see text], 4[Formula: see text]-(porphine-5,10,15,20 tetrayl) tetrakis (benzene sulfonic acid) have been investigated using density functional theory. The vibrational spectra of tetraphenylporphine and its substituted complex were simulated to study the substitution effects of sulfonic acid group at the peripheral sites of tetraphenylporphine. Experimentally, vibrational properties of these molecules have been studied using infrared absorption spectroscopic technique. The vibrational frequencies obtained from the theoretical studies generally agree with the experimental values. For substituted molecules, due to a change in charge distribution, ring vibrations accompanied by the S–O motions also appear at the higher wavenumbers. In the lower region, C–H bending vibrations diminish and SO3 group vibrations arise. The electronic absorption spectra of the substituted tetraphenylporphine in different solvents have been studied using UV-vis spectroscopy. In addition to dipole-dipole and electrostatic interactions, hydrogen bonding plays a key role in molecular-solvent interactions. The energy gap between the highest occupied and lowest unoccupied molecular orbitals and natural bonding orbital analysis show the intermolecular charge transfer interactions. The molecular electrostatic potential and solvent accessible surface area analysis were made in order to study the interaction sites of the molecules. The current-voltage characteristics for the substituted molecule were also plotted. It was found that substituted tetraphenylporphine show good photoconductivity.