title: Experimental and DFT studies on the vibrational and electronic spectra and NBO analysis of 2-amino-3-((E)-(9-p-tolyl-9H-carbazol-3-yl) methyleneamino) maleonitrile.
abstract: 2-Amino-3-((E)-(9-p-tolyl-9H-carbazol-3-yl) methyleneamino) maleonitrile (ACMM) was synthesized and characterized by X-ray diffraction, FT-IR, FT-Raman and UV-Vis spectra. The X-ray diffraction study showed that ACMM has a Z-configuration, due to the intramolecular C18H18A⋯N2, N3H3A⋯N2 and C20H20A⋯N4 hydrogen bonds and intermolecular C10H10A⋯N4, N3H3B⋯N9 (2-x, 2-y, 2-z) and N3H8C⋯N4 (2-x, 1-y, 2-z) hydrogen bonds. The benzene ring including methyl is twisted from the mean plane of the carbazole group by 59.7(3)°. Vibrational spectra and electronic spectra measurements were made for the compound. Optimized geometrical structure and harmonic vibrational frequencies were computed with DFT (B3-based B3P86, B3LYP, B3PW91 and B-based BP86, BLYP, BPW91) methods and ab initio RHF method using 6-311++G(d, p) basis set. Assignments of the observed spectra were proposed. The equilibrium geometries computed by all of the methods were compared with X-ray diffraction results. The absorption spectra of the title compound were computed both in gas phase and in DMF solution using TD-B3LYP/6-311++G(d, p) and PCM-B3LYP/6-311++G(d, p) approaches, respectively. The calculated results provide a good description of positions of the bands maxima in the observed electronic spectrum. Temperature dependence of thermodynamic parameters in the range of 100-1000K were determined. The bond orbital occupancies, contribution from parent natural bond orbital (NBO), the natural atomic hybrids was calculated and discussed.
authors.affiliation: Faculty of Chemistry, Northeast Normal University, Changchun 210009, PR China; Huaian Key Laboratory for Photoelectric Conversion and Energy Storage Materials, Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223300, Jiangsu, PR China.
authors.forename: Nana
authors.initials: N
authors.lastname: Meng
authors.affiliation: Huaian Key Laboratory for Photoelectric Conversion and Energy Storage Materials, Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223300, Jiangsu, PR China. Electronic address: yuzhang@hytc.edu.cn.
authors.forename: Yu
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Huaian Key Laboratory for Photoelectric Conversion and Energy Storage Materials, Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223300, Jiangsu, PR China.
authors.forename: Yiwei
authors.initials: Y
authors.lastname: Wang
authors.affiliation: Huaian Key Laboratory for Photoelectric Conversion and Energy Storage Materials, Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223300, Jiangsu, PR China.
authors.forename: Kuirong
authors.initials: K
authors.lastname: Ma
authors.affiliation: Huaian Key Laboratory for Photoelectric Conversion and Energy Storage Materials, Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223300, Jiangsu, PR China.
authors.forename: Jianying
authors.initials: J
authors.lastname: Zhao
authors.affiliation: Huaian Key Laboratory for Photoelectric Conversion and Energy Storage Materials, Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223300, Jiangsu, PR China.
authors.forename: Guodong
authors.initials: G
authors.lastname: Tang
mesh_terms: D002227:Carbazoles / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004583:Electrons; D019277:Entropy; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D055672:Static Electricity; D014732:Vibration
chemical_list: D002227:Carbazoles; D009570:Nitriles
keywords: 2-Amino-3-((E)-(9-p-tolyl-9H-carbazol-3-yl) methyleneamino) maleonitrile; Density functional theory (DFT); Electronic spectra; NBO; Vibrational spectra