Huang Qiu Ying, Zhao Yang, Meng Xiang Ru
Department of Chemical Engineering, Henan Polytechnic Institute, 473009 Nanyang, Henan, People's Republic of China.
Department of Chemical Engineering, Henan Vocational College of Applied Technology, 450042 Zhengzhou, Henan, People's Republic of China.
Acta Crystallogr C Struct Chem. 2017 Aug 1;73(Pt 8):645-651. doi: 10.1107/S2053229617010877. Epub 2017 Jul 31.
Careful choice of the organic ligands is one of the most important parameters in the rational design and synthesis of coordination polymers. Aromatic polycarboxylates have been widely used in the preparation of metal-organic polymers since they can utilize various coordination modes to form diverse structures and can act as hydrogen-bond acceptors and donors in the assembly of supramolecular structures. Nitrogen-heterocyclic organic compounds have also been used extensively as ligands for the construction of polymers with interesting structures. In the polymers catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN}cobalt(II)]-μ-benzene-1,4-dicarboxylato-κO:O] dihydrate], {[Co(CHO)(CHN)(HO)]·2HO}, (I), and catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN}nickel(II)]-μ-benzene-1,4-dicarboxylato-κO:O] dihydrate], {[Ni(CHO)(CHN)(HO)]·2HO}, (II), the Co or Ni ion lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry, coordinated by two N atoms from two imidazole rings and four O atoms from two monodentate carboxylate groups and two water molecules. The dicarboxylate ligands bridge metal ions forming a polymeric chain. The 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole ligands coordinate to the Co or Ni centres in monodentate modes through an imidazole N atom and are pendant on opposite sides of the main chain. The two structures are isomorphous. In the crystal, the one-dimensional chains are further connected through O-H...O, O-H...N and N-H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviours and fluorescence properties of both polymers have been investigated.
在配位聚合物的合理设计与合成中,仔细选择有机配体是最重要的参数之一。芳香多羧酸盐已被广泛用于金属有机聚合物的制备,因为它们可以利用各种配位模式形成多样的结构,并且在超分子结构组装中可作为氢键受体和供体。含氮杂环有机化合物也被广泛用作配体来构建具有有趣结构的聚合物。在聚合物链状聚[[[二水合双{2 - [(1H - 咪唑 - 1 - 基)甲基] - 6 - 甲基 - 1H - 苯并咪唑 - κN}钴(II)] - μ - 苯 - 1,4 - 二羧基 - κO:O]二水合物],{[Co(C₈H₁₀N₃)₂(H₂O)₂]·2H₂O},(I),和链状聚[[[二水合双{2 - [(1H - 咪唑 - 1 - 基)甲基] - 6 - 甲基 - 1H - 苯并咪唑 - κN}镍(II)] - μ - 苯 - 1,4 - 二羧基 - κO:O]二水合物],{[Ni(C₈H₁₀N₃)₂(H₂O)₂]·2H₂O},(II)中,Co或Ni离子位于一个对称中心上,并呈现出略微扭曲的八面体配位几何构型,由来自两个咪唑环的两个N原子以及来自两个单齿羧酸盐基团和两个水分子的四个O原子配位。二羧酸盐配体桥连金属离子形成聚合物链。2 - [(1H - 咪唑 - 1 - 基)甲基] - 6 - 甲基 - 1H - 苯并咪唑配体通过一个咪唑N原子以单齿模式与Co或Ni中心配位,并悬垂在主链的相对两侧。这两种结构是同构的。在晶体中,一维链通过O - H...O、O - H...N和N - H...O氢键进一步连接,形成三维超分子结构。此外,还研究了这两种聚合物的红外光谱性质、粉末X射线衍射图谱、热重行为和荧光性质。