Facile Synthesis, Spectral (IR, Mass, UV−Vis, NMR), Linear and Nonlinear Investigation of the Novel Phosphonate Compounds: A Combined Experimental and Simulation Study

Abstract

AbstractHerein, we reported the imino phosphonate compounds: (4‐methoxy‐benzylidene‐amino‐phenyl‐methyl‐phosphonic acid diethyl ester (MBPDE), 4‐hydroxy‐benzylidene‐amino‐phenyl‐methyl‐phosphonic acid diethyl ester (HBPDE) and 4‐hydroxy‐3‐methoxy‐benzylidene‐amino‐phenyl‐methyl‐phosphonic acid diethyl ester (HMBPD) form the chemical reaction of diethyl (α‐amino benzyl)phosphonate hydrochloride and substituted benzaldehyde. These compounds were characterized by various spectroscopic techniques: FT‐IR, Mass, UV–VIS, 1H NMR and 13 C NMR. Additionally, the optimized molecular structures, FT‐IR, natural bond orbitals (NBOs), frontier molecular orbitals (FMOs), non‐linear optical (NLO) properties were calculated by the density functional theory (DFT) using the B3LYP functional with the 6–311+G(d,p) basis set. Moreover, UV–Visible spectrum of MBPDE, HBPDE and HMBPD were predicted in different solvents using the time dependent TD‐DFT [B3LYP/6‐311+G(d,p)] method using Polarizable Continuum Model (PCM). The non‐linear optical (NLO) properties were calculated by M06 functional with the 6–311+G(d,p) basis set. A synergistic relationship is observed between the experimental and theoretical findings. NBO analysis provided insights about the stability and charge delocalization of the entitled molecules. The global reactivity descriptors were achieved through HOMO‐LUMO energies. The efficiency of the entitled molecules concerning charge transfer and participation in diverse chemical reactivities were figured out perceptibly by applying the frontier molecular orbitals (FMOs) analysis. The average polarizability values: 277.184, 261.332 and 280.254 a.u. of the MBPDE, HBPDE and HMBPD were determined respectively. The total first hyperpolarizability (βtot) values of the MBPDE, HBPDE and HMBPD were also obtained to be 992.900, 781.527 and 1107.526 a.u. respectively. The compound HMBPD comprising of higher magnitude of average polarizability and the total first hyperpolarizability (βtot) values than MBPDE and HBPDE molecules. Moreover, NLO properties of urea molecule were found smaller in comparison to the MBPDE, HBPDE and HMBPD. The medicinal importances of these novel compounds as well as its contribution towards nonlinear optical field are our future targets.