[Co^(Ⅲ)(DIEN)(N_(3))_(3)]配合物的合成、晶体结构及量子化学研究

Synthesis,Crystal Structure and Quantum Chemistry Study on [Co~Ⅲ(DIEN)(N_3)_3] Complex

采用配体占位策略和分子自组装原理,选用二亚乙基三胺(DIEN)为有机配体,Co^(3+)为中心金属离子,室温下,通过溶液法合成了一例单核钴配合物[Co^(Ⅲ)(DIEN)(N_(3))_(3)](1)单晶体,利用X射线单晶衍射方法、元素分析和量子化学计算对配合物进行了结构表征和电子结构分析。结构解析表明,该配合物单晶体属于三斜晶系,■空间群,晶胞参数为: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)nm^(3)。中心金属离子Co(Ⅲ)位于拉长八面体配位环境中,每个配合物分子由一个Co(Ⅲ)离子、3个叠氮阴离子和1个二亚乙基三胺组成,一个叠氮离子的两个N原子位置无序,占有率各为50%。单核结构之间通过N—H…N分子间氢键和π…π堆积组装成一维链状超分子结构。此外,以X射线衍射分析得到的晶体结构为计算模型,采用密度泛函理论(DFT)对配合物1的几何构型进行了全构型结构优化和振动频率计算,分析了配合物的单点能、原子电荷分布及前线分子轨道等性质。量子化学计算结果表明该配合物构型为稳定构型,且与实验结果相吻合。

Adopting ligand occupation strategy and the principle of molecular self-assembly,a mononuclear cobalt(Ⅲ) complex [Co~Ⅲ(DIEN)(N_(3))_(3)](1,DIEN=diethylenetriamine) was synthesized by solution method using diethylenetriamine as the organic ligand and Co^(3+) 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 ■ 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) nm~3.The central ion Co(Ⅲ) has an elongated octahedral configuration.Each complex is composed of Co^(3+) 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.