title: A combined experimental and DFT study of a novel unsymmetrical azine 2-(4-methoxybenzylidene)-1-(1-(4-isobutylphenyl) ethylidene) hydrazine.
abstract: A novel unsymmetrical azine 2-(4-methoxybenzylidene)-1-(1-(4-isobutylphenyl) ethylidene) hydrazine (UA) was prepared and characterized by IR, (1)H and (13)C NMR spectral studies. A 2D - potential energy scan (PES) of p-isobutylacetophenone (IBAP) was the portal to the conformational analysis of UA by density functional theory (DFT) methods using 6-31G(d,p) basis set by Gaussian 03 program. The theoretical IR frequencies were found to be in good agreement with the experimental values. The IR frequencies of UA were analyzed by means of Potential energy Distribution (PED %) calculation using Vibrational Energy Distribution Analysis (VEDA 4) program. The experimental NMR chemical shift values of UA were compared with the theoretical values obtained by DFT method. Nonlinear optical behavior of the unsymmetrical azine is also examined by the theoretically predicted values of dipole moment (μ), polarizability (α0) and first hyperpolarizability (βtot). Stability of the UA molecule has been analyzed using NBO analysis. The electrochemistry of UA studied experimentally by cyclic voltammetry is complemented by the computational analysis of the anionic form of the molecule UA. The determination of various global and local reactivity descriptors in the context of chemical reactivity is also performed and the electrophilicity at the vital atomic sites in UA is revealed. Bader's Atoms in molecules (AIM) theory of UA indicated the presence of intramolecular hydrogen bonding in the molecule. The molecular electrostatic potential (MEP) and HOMO-LUMO orbital analysis are also performed for the molecule UA.
authors.affiliation: Department of Chemistry, Annamalai University, Chidambaram 608 002, India.
authors.forename: P
authors.initials: P
authors.lastname: Vijaya
authors.affiliation: Department of Chemistry, Annamalai University, Chidambaram 608 002, India.
authors.forename: K R
authors.initials: KR
authors.lastname: Sankaran
mesh_terms: D001391:Azo Compounds; D001593:Benzyl Compounds / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D004563:Electrochemistry / Q000379:methods*; D006834:Hydrazines / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D017711:Nonlinear Dynamics; D016011:Normal Distribution; D013053:Spectrophotometry / Q000379:methods*; D013055:Spectrophotometry, Infrared / Q000379:methods; D055672:Static Electricity; D013816:Thermodynamics; D014732:Vibration
chemical_list: C000603912:2-(4-methoxybenzylidene)-1-(1-(4-isobutylphenyl)ethylidene)hydrazine; D001391:Azo Compounds; D001593:Benzyl Compounds; D006834:Hydrazines; C029424:hydrazine; D002244:Carbon; D006859:Hydrogen
keywords: AIM; DFT; NBO; Potential energy scan; VEDA