An Experimental and Computational Exploration on the Electronic, Spectroscopic, and Reactivity Properties of Novel Halo-Functionalized Hydrazones

Abstract

Herein, halo-functionalized hydrazone derivatives “2-[(6′-chloroazin-2′-yl)oxy]- N ′-(2-fluorobenzylidene) aceto-hydrazone ( CPFH ), 2-[(6′-chloroazin-2′-yl)oxy]- N ′-(2-chlorobenzylidene) aceto-hydrazones ( CCPH ), 2-[(6′-chloroazin-2′-yl)oxy]- N ′-(2-bromobenzylidene) aceto-hydrazones ( BCPH )” were synthesized and structurally characterized using FTIR, 1 H-NMR, 13 C-NMR, and UV–vis spectroscopic techniques. Computational studies using density functional theory (DFT) and time dependent DFT at CAM-B3LYP/6-311G (d,p) level of theory were performed for comparison with spectroscopic data (FT-IR, UV–vis) and for elucidation of the structural parameters, natural bond orbitals (NBOs), natural population analysis, frontier molecular orbital (FMO) analysis and nonlinear optical (NLO) properties of hydrazones derivatives ( CPFH , CCPH , and BCPH ). Consequently, an excellent complement between the experimental data and the DFT-based results was achieved. The NBO analysis confirmed that the presence of hyper conjugative interactions was pivotal cause for stability of the investigated compounds. The energy gaps in CPFH , CCPH , and BCPH were found as 7.278, 7.241, and 7.229 eV, respectively. Furthermore, global reactivity descriptors were calculated using the FMO energies in which global hardness revealed that CPFH was more stable and less reactive as compared to BCPH and CCPH . NLO findings disclosed that CPFH , CCPH , and BCPH have superior properties as compared to the prototype standard compound, which unveiled their potential applications for optoelectronic technology.

Exploration of Chromone-Based Thiosemicarbazone Derivatives: SC-XRD/DFT, Spectral (IR, UV–Vis) Characterization, and Quantum Chemical Analysis

“…The theoretical and experimental communities use vibrational spectroscopy as a method to investigate the molecular vibrations. 45 Similarly, DFT analysis for vibrational absorption spectroscopy is utilized to examine the existence of the vibrational modes for compounds 3a and 3b using the DFT/B3LYP/6-311+G(d,p) functional, and the results are listed in Tables S5 and S6 (Supporting Information), while their experimentally determined absorption frequencies and spectra are shown in Figures S1 and S2. In general, due to a well-known systematic error of anharmonicity and basis set deficiencies, the DFT hybrid B3LYP functional overrates the vibrational wavenumbers compared to the experimental results.…”

Facile Synthesis of Diversely Functionalized Peptoids, Spectroscopic Characterization, and DFT-Based Nonlinear Optical Exploration

“…FMO analysis is mostly used to explain different properties like reactivity, molecular interactions, electronic features, chemical stability, and charge transfer in different compounds. − Various chemists and physicists have exercised FMO investigation to expose the structural and geometrical characteristics of investigated systems. − The aptitude of a molecule to donate or accept the charge density is estimated through FMOs (HOMO and LUMO) energies. , Moreover, the energy gap between HOMO and LUMO ( E g = E LUMO – E HOMO ) is a key sign for nonlinear optical behavior of a compound and also used to gauge several parameters including chemical reactivity, ionization potential, chemical hardness, and chemical softness. A compound is considered soft, least stable, and highly reactive if it has a narrow HOMO–LUMO energy gap and vice versa. , FMO results of 1–4 are presented in Table .…”

Synthesis, Characterization, Computational, Antioxidant and Fluorescence Properties of Novel 1,3,5-Trimesic Hydrazones Derivatives

“…A wide range of triazine and hydrazone-containing molecules has been studied using DFT methods. Computational analysis is carried out to confirm the experimental findings and to investigate further structural features [19,20,21].…”