Adopting ligand occupation strategy and the principle of molecular self-assembly,a mononuclear cobalt(Ⅲ)complex[CoⅢ(DIEN)(N3)3](1,DIEN=diethylenetriamine)was synthesized by solution method using diethylenetriamine as the organic ligand and Co3+as the central metal ion at room temperature.Single crystal of complex 1 was obtained.The structural characterization and electronic structure analysis were carried out through X-ray single crystal diffraction,elemental analysis,and quantum chemical calculations.Single crystal X-ray diffraction analysis reveals that complex 1 is triclinic,space group of P(1)with a=0.825 3(2)nm,b=0.892 0(3)nm,c=0.898 7(3)nm,α=106.497(4)°,β=90.281(4)°,γ=113.861(4)°,V=0.574 7(3)nm3.The central ion Co(Ⅲ)has an elongated octahedral configuration.Each complex is composed of Co3+cation,three azide anions and one diethylenetriamine ligand.A disordered azide anion has a site occupancy of 50％,and 1D chain-like supermolecular was formed by N—H … N hydrogen bond and π … π packing interations.In addition,based on crystal structure of complex 1 determined by X-ray crystallographic analysis,the full geometry optimized and frequency calculations have been performed by density functional theory.The single-point energy,atomic charges and frontier molecular orbital were analyzed.The theoretical calculation results indicate that the complex configuration is stable and consistent with the experimental results.
关键词
钴(Ⅲ)超分子配合物/晶体结构/量子化学计算/密度泛函理论/原子电荷/前线分子轨道
Key words
Co(Ⅲ)supramolecular complex/crystal structure/quantum chemical calculation/density functional theory/atomic charge/frontier molecular orbital
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