以二羧酸二苯甲醚和吡啶基三唑为配体构筑的钴Ⅱ配合物的合成、结构、热稳定性及 DFT 计算(英文)

Synthesis, Structure, Thermostability and DFT Calculations of a Cobalt(Ⅱ) Coordination Compound Comstructed by Oxybis(benzoic acid) and Pyridyl-triazole

基于V型配体4,4′-二羧酸二苯甲醚(H2oba)和刚性配体3-(3吡啶基)-5-(4′吡啶基)-1-H-1,2,4三唑(3,4′-Hbpt),在水热条件下与醋酸钴制备了一种新的配位聚合物[Co(oba)(3,4′-Hbpt)]·H2O,并对其进行X-射线单晶衍射、热重分析、元素分析和红外光谱表征。配合物为单斜晶系,P21/c空间群,完全脱质子的oba2-配体的2个羧基连接Co髤离子形成八元环,3,4′-Hbpt配体和H2oba桥连2个Co髤形成二十五元环。相邻的八元环和二十五元环进一步通过oba2-作支柱连接,形成了二维的层-孔结构。采用密度泛函理论(DFT)方法,在B3LYP/6-31*G(d)和6-31**G(d,p)水平上对配体H2oba结构进行优化计算,探讨了其稳定性,前线轨道以及最优构型,计算结果与化合物1中H2oba的构象一致。

A new coordination polymer, [Co（oba）（3,4＇-Hbpt）]·H2O （H2oba=4,4＇ -oxybis （benzoic acid） and 3,4＇-Hbpt=3-（3-pyridyl）-5-（4＇-pyridyl）-1-H-1,2,4-triazole）, was prepared in the presence of V-shaped ligand H2oba, rigid ligand 3,4＇-Hbpt and cobalt acetate by hydrothermal reactions. The title complex was characterized by single-crystal X-ray diffraction, thermogravimetric analyses, elemental analysis and IR spectroscopy. It belongs to monoclinic system, space group P21/c. In the complex, the Co（Ⅱ） ions are linked by two carboxylate groups from protonated V-shaped oba2- to form an 8-membered ring. Then, oba2-, 3,4＇-Hbpt connect adjacent Co（Ⅱ） ions to form a 25-membered ring. Furthermore, the adjacent eight-membered and 25-membered rings are connected by oba2- pillars to form a 2D layer-hole in the structure. In addition, theoretical calculation based on density functional theory （DFT） at B3LYP/6-31G＊（d） and 6-31G＊＊（d,p） level is also employed to explicate the most optimized conformation, and investigate stability, frontier orbitals and the optimal configuration of H2oba, which is corresponded with experimental conformation. CCDC： 930887.