4,4′-联吡啶桥联的钴配位聚合物的合成、表征及量子化学计算

摘要/Abstract

摘要： 本文通过溶剂热法以对甲基苯磺酸钠为主配体,4,4′-联吡啶为辅助配体制备了一种结构新颖的钴配位聚合物{[Co(4,4′-bipy)(H₂O)₄]·(p-CH₃C₆H₄SO₃)₂}_n。通过红外光谱、X射线单晶衍射、热重分析、X射线粉末衍射等方法对钴配位聚合物进行了表征。结果表明,{[Co(4,4′-bipy)(H₂O)₄]·(p-CH₃C₆H₄SO₃)₂}_n属于单斜晶系,P2₁/c空间群,晶胞参数为a=11.319 1(14) Å,b=8.062 6(11) Å,c=14.936(2) Å,α=90°,β=92.423(4)°,γ=90°,V=1 361.9(3) Å³,Z=2。中心金属Co(Ⅱ)离子为六配位略有畸变的八面体构型,通过4,4′-联吡啶中的N原子桥联形成一维无限链状,层间通过配位水分子与对甲基苯磺酸之间的氢键作用进一步扩展成三维超分子结构。并运用Gaussian 09程序对钴配位聚合物中[Co(4,4′-bipy)₂(H₂O)₄]·(p-CH₃C₆H₄SO₃)结构单元进行了量子化学计算,获得了优化构型。原子电荷分布及前沿占据轨道组成很好地佐证了晶体结构的配位环境。电化学阻抗测试结果证明该配位聚合物的电阻较小,导电性能良好,为其在电化学应用方面提供了一定的理论依据。

关键词: 钴配位聚合物, 溶剂热法, 晶体结构, 4,4′-联吡啶, 量子化学计算

Abstract: A novel structure cobalt coordination polymer of {[Co(4,4′-bipy)(H₂O)₄]·(p-CH₃C₆H₄SO₃)₂}_n was prepared by solvothermal method with sodium p-toluenesulfonate as the main ligand and 4,4′-bipy as the auxiliary ligand. The cobalt coordination polymer was characterized by infrared spectroscopy, X-ray single crystal diffraction, thermogravimetric analysis and X-ray powder diffraction. The results show that {[Co(4,4′-bipy)(H₂O)₄]·(p-CH₃C₆H₄SO₃)₂}_n belongs to monoclinic system, P2₁/c space group; cell parameters of a=11.319 1(14)Å, b=8.062 6(11)Å, c=14.936(2)Å, α=90°, β=92.423(4)°, γ=90°, V=1 361.9(3)Å³, Z=2. The central metal Co(Ⅱ) ion is a hexagonal octahedral structure with slightly distorted coordination. It forms a one-dimensional infinite chain through the bridging of N atoms in 4,4′-bipy. The interlayer is further expanded into a three-dimensional supramolecular structure through the hydrogen bonding between the coordination water molecule and p-methylbenzenesulfonic acid. The [Co(4,4′-bipy)₂(H₂O)₄]·(p-CH₃C₆H₄SO₃) structural unit in the cobalt coordination polymer was quantum chemically calculated by Gaussian 09 program, and the optimal configuration was obtained. The atomic charge distribution and the composition of the front occupied orbital well support the coordination environment of the crystal structure. Finally, the electrochemical impedance test shows that the resistance of the coordination polymer is small and the conductivity is good, which provides a certain theoretical basis for its electrochemical application.

Key words: cobalt coordination polymer, solvothermal method, crystal structure, 4,4′-bipy, quantum chemical calculation

中图分类号:

O614.4

史燚威, 杨瑞杰, 张迎春, 王鑫, 王敏, 宋志国. 4,4′-联吡啶桥联的钴配位聚合物的合成、表征及量子化学计算[J]. 人工晶体学报, 2024, 53(9): 1583-1590.

SHI Yiwei, YANG Ruijie, ZHANG Yingchun, WANG Xin, WANG Min, SONG Zhiguo. Synthesis, Characterization and Quantum Chemical Calculation of Cobalt Coordination Polymer with 4,4′-bipy Bridge[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1583-1590.

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