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)
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摘要
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髤 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 髤 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/6-31*G(d) and 6-31**G(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.
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髤 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 髤 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/6-31*G(d) and 6-31**G(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.
引文
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[9]Li B,Chen S P,Xie G,et al.Struc.Chem.,2012,23(2):417-423
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[11]Mahata P,Madras G,Natarajan S.J.Phys.Chem.B,2006,110(28):13759-13768
[12]Wen G L,Wang Y Y,Wang H,et al.J.Mole.Struc.,2009,928:125-131
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