Solvent effect, DFT and NLO studies of A–π–D–π–A and A–π–D–π–D push–pull chromophore of 1,2-diazepin-4-ol based derivatives with optical limiting application

The nonlinear optical properties of push–pull chromophores, namely (E)-7-(4-bromophenyl)-2,5-bis(4-nitrophenyl)-3,4,5,6-tetrahydro-2H-1,2-diazepin-4-ol (A–π–D–π–A) and (E)-7-(4-bromophenyl)-5-(4-nitrophenyl)-2-phenyl-3,4,5,6-tetrahydro-2H-1,2-diazepin-4-ol (A–π–D–π–D), have been investigated using the z-scan technique. NMR, FT-IR, and UV–visible spectral analysis have been performed. The results were compared with density functional theory calculations employing the B3LYP/6-311++G (d, p) basis set. Geometry optimization, frontier molecular analysis, and TD-DFT calculations were conducted in various solvent environments to elucidate solute–solvent interactions. Gaussian 09 software was employed for natural bond orbital analysis, natural population analysis, and molecular electrostatic potential exploration. This comprehensive approach provides insights into the molecular structure and electronic properties of the investigated chromophores, shedding light on their potential applications in nonlinear optics. Normal coordinate analysis using the MOLVIB software has been used to assign the vibrational mode unambiguously. Theoretical second-order hyperpolarizability was computed, and NLO investigations have been employed to determine the second-order hyperpolarizability in both the polar and non-polar solvents. Further, the optical limiting capability was also examined.