Crystal growth, structural and DFT study of novel single crystal (E)-N′-(2-chlorobenzylidene)-4-fluorobenzohydrazide for nonlinear optical applications

Nonlinear optical (NLO) material, (E)-N'-(2-chlorobenzylidene)-4-fluorobenzohydrazide (CBBH) novel single crystal was grown via a Schiff base chemical reaction. A single crystal X-ray diffraction technique was utilized for the recognition of the crystal structure of the CBBH. The imperfection of novel CBBH crystal was checked by high resolution X-ray diffraction (HRXRD) study. Hirshfeld surface study through colour coding was applied to know the intra and intermolecular force interactions. Fourier transforms infrared (FTIR), proton 1H and carbon C-13 nuclear magnetic resonance (NMR) spectra were employed to elucidate the various functional groups and structure of the crystal. The absorption maxima from UV-Vis plot for the CBBH molecule was found at 314 nm, which reveals the pi-pi* transition. Photololuminescence (PL) study reveals that emission observed in the blue-violet region. The HOMO and LUMO energies were investigated using the density functional theory (DFT) method. Natural bond orbital (NBO) analysis explored the donor-acceptor exchanges and it's endurance into intra-molecularly. The first-order hyperpolarizability value, beta(0) = 23.73 x 10(30) esu was observed for CBBH crystal, which is similar to 64 times larger than that of urea molecule (0.3728 x 10(30) esu). Z-scan experiment on CBBH crystal supports its third-order nonlinear optical (NLO) properties. Optical limiting analysis indicates reverse saturation absorption behavior of CBBH crystal.

Automated summary

A novel single crystal (E)-N'-(2-chlorobenzylidene)-4-fluorobenzohydrazide (CBBH) was grown using a Schiff base chemical reaction and its crystal structure was recognized by single crystal X-ray diffraction. The imperfection of the crystal was checked by high resolution X-ray diffraction. Hirshfeld surface study was applied to investigate intra and intermolecular force interactions. Various techniques including FTIR, proton 1H and carbon C-13 NMR spectra were employed to determine the structure and functional groups of the crystal. The crystal exhibited nonlinear optical properties, as confirmed by photoluminescence, density functional theory simulation, natural bond orbital analysis, and Z-scan experiment.