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由三联苯-2,5,2',5'-四羧酸和双(咪唑)桥连配体构建的五种金属有机框架的合成、晶体结构及紫外可见吸收性质

Syntheses, crystal structures and UV-visible absorption properties of five metal-organic frameworks constructed from terphenyl-2,5,2',5'-tetracarboxylic acid and bis(imidazole) bridging ligands.

作者信息

Fan Liming, Zhang Xiutang, Zhang Wei, Ding Yuanshuai, Fan Weiliu, Sun Liming, Pang Yue, Zhao Xian

机构信息

State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.

出版信息

Dalton Trans. 2014 May 14;43(18):6701-10. doi: 10.1039/c3dt53379d.

Abstract

The solvothermal reactions of terphenyl-2,5,2',5'-tetracarboxylic acid (H4tptc) and transition metal cations (Ni(II), Mn(II)) afford five novel coordination polymers (CPs) in the presence of four bis(imidazole) bridging ligands (1,3-bimb = 1,3-bis(imidazol-1-ylmethyl)benzene, 1,4-bmib = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, 4,4'-bibp = 4,4'-bis(imidazol-1-yl)biphenyl, 4,4'-bimbp = 4,4'-bis(imidazol-1-ylmethyl)biphenyl), namely, [M(tptc)(0.5)(1,3-bimb)(H2O)]n (M = Ni for 1, Mn for 2), {[Ni(tptc)(0.5)(1,4-bmib)]·0.25H2O}n (3), {[Ni(tptc)(0.5)(4,4'-bibp)2(H2O)]·2H2O}n (4) and {[Ni(tptc)(0.5)(4,4'-bimbp)(1.5)(H2O)]·H2O}n (5). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes 1 and 2 are isomorphous and exhibit a 3D (3,4)-connected tfi framework with the point Schläfli symbol of (4·6(2))(4·6(6)·8(3)). Complex 3 shows an unprecedented 3D (4,4)-connected framework with the point Schläfli symbol of (4·6(4)·8(2))2(4(2)·8(4)). Complex 4 displays a novel 2D self-catenating 5-connected network with the Schläfli symbol of (4(6)·6(4)) based on three interpenetrating 4(4)-sql subnets. Complex 5 features a 2D 3-connected 6(3)-hcb network built from interesting chains with loops. To the best of our knowledge, the 3D (4,4)-connected (4·6(4)·8(2))2(4(2)·8(4)) host-framework of 3 and 2D self-catenating 5-connected (4(6)·6(4)) network of 4 have never been documented to date. Moreover, the UV-Visible absorption spectra of complexes 1-5 have been investigated.

摘要

在四个双(咪唑)桥联配体(1,3 - bimb = 1,3 - 双(咪唑 - 1 - 基甲基)苯、1,4 - bmib = 1,4 - 双(2 - 甲基咪唑 - 1 - 基甲基)苯、4,4' - bibp = 4,4' - 双(咪唑 - 1 - 基)联苯、4,4' - bimbp = 4,4' - 双(咪唑 - 1 - 基甲基)联苯)存在的情况下,三联苯 - 2,5,2',5' - 四羧酸(H4tptc)与过渡金属阳离子(Ni(II)、Mn(II))发生溶剂热反应,得到了五种新型配位聚合物(CPs),即[M(tptc)(0.5)(1,3 - bimb)(H2O)]n(M = Ni时为1,M = Mn时为2)、{[Ni(tptc)(0.5)(1,4 - bmib)]·0.25H2O}n(3)、{[Ni(tptc)(0.5)(4,4' - bibp)2(H2O)]·2H2O}n(4)和{[Ni(tptc)(0.5)(4,4' - bimbp)(1.5)(H2O)]·H2O}n(5)。通过单晶X射线衍射分析确定了它们的结构,并通过元素分析、红外光谱、粉末X射线衍射(PXRD)和热重(TG)分析进一步进行了表征。配合物1和2是同构的,呈现出具有点Schläfli符号为(4·6(2))(4·6(6)·8(3))的三维(3,4)连接的tfi框架。配合物3展示了一种前所未有的具有点Schläfli符号为(4·6(4)·8(2))2(4(2)·8(4))的三维(4,4)连接框架。配合物4基于三个互穿的4(4)-sql子网展示了一种具有Schläfli符号为(4(6)·6(4))的新型二维自连环5连接网络。配合物5具有由有趣的带环链构建的二维3连接6(3)-hcb网络。据我们所知,配合物3的三维(4,4)连接(4·6(4)·8(2))2(4(2)·8(4))主框架和配合物4的二维自连环5连接(4(6)·6(4))网络迄今为止从未有过文献记载。此外,还研究了配合物1 - 5的紫外可见吸收光谱。

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