An analysis of spectroscopic, computational and biological activity studies of L-shaped sulfamoylbenzoic acid derivatives: a third order nonlinear optical material

Abstract

The current article focuses mainly on investigation of structural, reactivity, topology studies, and third order nonlinear optical properties of the synthesized 2-(benzylamino)-4-chloro-5-sulfamoylbenzoic acid (BACSBA) with the aid of spectroscopic techniques and computational methods. The structure in the solid state was obtained unambiguously by SCXRD study that revealed that BACSBA has L-shaped structure stabilized by NeH/O intramolecular hydrogen bond. Further, the two dimensional sheet like architecture formation by linking of molecules via OeH/O and NeH/O hydrogen bonds, were visualized both qualitatively and quantitatively by Hirshfeld surface analysis. Also, a topological analysis made through Quantum Theory of Atoms In Molecules (QTAIM) highlights the observations NeH/O bonds on solid state. The quantum chemical calculation was performed at DFT/6e311þþG (d,p) level of basis set. The analysis of each vibrational wave number was performed with the help of potential energy distribution (PED) using VEDA4 software and correlation with experimental data shows good concurrence. The reactive sites have been predicted and visualized by molecular electrostatic surface potential (MESP) and Fukui function calculation, together with hydrogen bond dissociation energy (H-BDE) for the BACSBA compound. Frontier molecular orbitals (FMO), global reactivity parameters, natural bond orbital analysis (NBO), localized orbital locator (LOL) and electron localization function (ELF) properties have also been studied for the titled compound. The super molecule (SM) approach with 372,680 atoms at the DFT/ CAM-B3LYP/6e311þþG (d,p) level was used for calculating the nonlinear optical properties of the crystal. The electrical parameters such as total dipole moment, average linear polarizability and average second IDRI hyperpolarizability were calculated. In addition, the linear refractive index and the nonlinear third order macroscopic susceptibility of the crystal was estimated as a function of the frequency of the applied electric field. The value of third order nonlinear susceptibility for the BACSBA crystal at 532 nm was found to be 45.57 times greatest than the experimentally measured result of organic crystal (2E)-1- (3-bromophenyl)-3-[4 (methylsulfanyl)phenyl]prop-2-en-1-one (3Br4MSP) demonstrating that BACSBA crystal could be a good potential candidate for nonlinear optical applications. In addition, the thermal stability was studied showing that the crystal as potential optical devices at temperature up to 234 C.