An analysis of structural and spectroscopic signatures, the reactivity study of synthetized 4,6-dichloro-2-(methylsulfonyl)pyrimidine: A potential third-order nonlinear optical material

Abstract

In this work the 4,6-dichloro-2-(methylsulfonyl)pyrimidine (DCMSP) has been synthesized from 4,6-dichloro-2-(methylthio)pyrimidine, its molecular and electronic structure was authenticated by detailed spectroscopic signature studies (via SCXRD, FT-Raman, FT-IR and (1H &13C) NMR), Hirshfeld surface analysis and DFT calculations. The solid-state crystal structure of DCMSP corroborated by the single crystal X-ray diffraction studies, features CH⋯O and π···π interactions. Quantum chemical calculations of DCMSP have been performed at DFT/B3LYP/6-311++G (d,p) level of theory. The detailed assignment of each the vibrational mode was done on the basis of potential energy distribution (PED) by using the VEDA4 program and these results have been correlated with the experimental data. We calculated the linear and nonlinear optical properties of the title compound to understand the linear and nonlinear optical behavior in both static and dynamic fields using an iterative electrostatic embedding scheme and density functional theory (DFT) methods with standard and long-range corrected functionals. We also performed a study of the linear refractive index and nonlinear optical susceptibility χ(3) of the crystal as a function of frequency. An estimate of linear and nonlinear macroscopic quantities confirms their suitability for nonlinear optical devices such as optical limiting and optical switching. Investigation of local and global reactivity parameters of DCMSP was carried out by the calculation of molecular electrostatic potential (MEP), average local ionization energies (ALIE) surfaces and atomic Fukui indices in the gas phase. Stability in water and sensitivity towards autoxidation process has been investigated by radial distribution function (RDF) and bond dissociation energies (BDE) calculation after molecular dynamic simulations.