title: The spectroscopic (FT-IR, UV-vis), Fukui function, NLO, NBO, NPA and tautomerism effect analysis of (E)-2-[(2-hydroxy-6-methoxybenzylidene)amino]benzonitrile.
abstract: A new o-hydroxy Schiff base, (E)-2-[(2-hydroxy-6-methoxybenzylidene)amino]benzonitrile was isolated and investigated by experimental and theoretical methodologies. The solid state molecular structure was determined by X-ray diffraction method. The vibrational spectral analysis was carried out by using FT-IR spectroscopy in the range of 4000-400cm(-)(1). Theoretical calculations were performed by density functional theory (DFT) method using 6-31G(d,p) basis set. The results of the calculations were applied to simulated spectra of the title compound, which show excellent agreement with observed spectra. The UV-vis spectrum of the compound was recorded in the region 200-800 nm in several solvents and electronic properties such as excitation energies, and wavelengths were calculated by TD-DFT/B3LYP method. The most prominent transitions were corresponds to π→π∗. Hybrid density functional theory (DFT) was used to investigate the enol-imine and keto-amine tautomers of titled compound. The titled compound showed the preference of enol form, as supported by X-ray and spectroscopic analysis results. The geometric and molecular properties were compaired for both enol-imine and keto-amine forms. Additionally, geometry optimizations in solvent media were performed with the same level of theory by the integral equation formalism polarizable continuum (IEF-PCM). Stability of the molecule arises from hyperconjugative interactions, charge delocalization and intramolecular hydrogen bond has been analyzed using natural bond orbital (NBO) analysis. Mulliken population method and natural population analysis (NPA) have been studied. Also, condensed Fukui function and relative nucleophilicity indices calculated from charges obtained with orbital charge calculation methods (NPA). Molecular electrostatic potential (MEP) and non linear optical (NLO) properties are also examined.
authors.affiliation: Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey. Electronic address: zeynep.kelesoglu@omu.edu.tr.
authors.forename: Zeynep
authors.initials: Z
authors.lastname: Demircioğlu
authors.affiliation: Department of Chemistry, Faculty of Arts and Science, Sinop University, TR-57000 Sinop, Turkey.
authors.forename: Çiğdem Albayrak
authors.initials: ÇA
authors.lastname: Kaştaş
authors.affiliation: Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey.
authors.forename: Orhan
authors.initials: O
authors.lastname: Büyükgüngör
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D017711:Nonlinear Dynamics; D055620:Optical Phenomena; D011789:Quantum Theory; D012545:Schiff Bases / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D055672:Static Electricity; D013237:Stereoisomerism; D014732:Vibration
chemical_list: D009570:Nitriles; D012545:Schiff Bases; D012997:Solvents; C014356:benzonitrile
keywords: Fukui function analysis; Mulliken electronegativity; Natural bond orbital analysis (NBO); Natural population analysis (NPA); Nonlinear optical properties (NLO)