title: Theoretical investigations of the structures and electronic spectra of Zn(II) and Ni(II) complexes with cyclohexylamine-N-dithiocarbamate.
abstract: The ground-state structures of two ligands cyclohexylamine-N-dithiocarbamate (L) and PPh3 and four complexes [Zn(L)2] (A), [Ni(L)2] (B), [Zn(L)2PPh3] (C), and [Ni(L)2PPh3] (D) are optimized by M06, B3LYP, and B3PW91 methods with the same mixed basis set. As compared with the experimental data of other complexes containing the Ni-P bond, the result obtained by M06/6-31+G(d)-LANL2DZ method is finally regarded as accurate and reliable for this project. Based on the optimized geometries, the compositions of molecular orbitals are analyzed and the absorption spectra are simulated. When one more ligand PPh3 is coordinated, the lowest-lying transition energy presents red-shift; while it shows blue-shift when the metal coordination center change from Ni to Zn with the same ligands. The detailed transition characters related with the absorption spectrum are assigned. In all the key transitions, it is hard to find the contribution from Zn atom. On the contrary, the d orbital of Ni atom contributes a lot for the HOMO and LUMO of complexes B and D. Consequently, the transition characters of Zn(II) and Ni(II) complexes are different.
authors: Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, PR China.
authors: Xiaohan
authors: X
authors: Yu
authors: Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, PR China.
authors: Na
authors: N
authors: Wang
authors: Wuhan Center for Magnetic Resonance, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, PR China.
authors: Hongqing
authors: H
authors: He
authors: Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, PR China. Electronic address: chemwangl@henu.edu.cn.
authors: Li
authors: L
authors: Wang
mesh_terms: D065966:Absorption, Physicochemical; D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry*; D003514:Cyclohexylamines / Q000737:chemistry*; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004583:Electrons; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D013057:Spectrum Analysis; D013816:Thermodynamics; D013859:Thiocarbamates / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D003514:Cyclohexylamines; D013859:Thiocarbamates; C000593896:cyclohexylamine-N-dithiocarbamate; D009532:Nickel; D015032:Zinc; D004121:Dimethyl Sulfoxide
keywords: Cyclohexylamine-N-dithiocarbamate; Ni(II) complex; Spectroscopy; TD-DFT; Zn(II) complex