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由3,3',5,5'-联苯四甲酸原始配体合成的四种配位聚合物的结构多样性及相关性质

Structural diversities and related properties of four coordination polymers synthesized from original ligand of 3,3',5,5'-azobenzenetetracarboxylic acid.

作者信息

Fan Liming, Fan Weiliu, Li Bin, Liu Xinzheng, Zhao Xian, Zhang Xiutang

机构信息

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

出版信息

Dalton Trans. 2015 Feb 7;44(5):2380-9. doi: 10.1039/c4dt03076a.

Abstract

Four new coordination polymers, namely [Co(H2O2abtc)(bibp)]n (), {[Mn1.5(Oabtc)(H2O)2]·(H2bmib)0.5·H2O}n (), {[Cd1.5(O2abtc)]·(H2bmib)0.5·2H2O}n (), and {[Cd(nip)(bibp)]·0.5H2O}n (),were constructed under solvothermal conditions in the presence of two bis(imidazole) bridging linkers (bimb = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, bibp = 4,4'-bis(imidazol-1-yl)biphenyl). The unstable azo ligand of 3,3',5,5'-azobenzenetetracarboxylic acid (H4abtc) could be oxidized and resulted in three oxidized derivatives of H4Oabtc (one N atom was oxidized), H4O2abtc (two N atoms were oxidized), and H2nip (one H4abtc was oxidized to two 5-nitroisophthalic acids). Their structures were determined by single-crystal X-ray diffraction and further characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complex exhibited an interestingly 2D + 2D → 3D parallel entangled network based on 4-connected (4(4)·6(2))-sql sheets. Complex was found to be a {Mn3(COO)6} trinuclear SBU based 2D (3,6)-connected (4(3))2(4(6)·6(6)·8(3))-kgd sheet. While complex displays a {Cd3(COO)8} trinuclear SBUs based 3D (4,8)-connected (4(6))2(4(12)·6(12)·8(4))-flu network. Complex can be regard as a {Cd2(COO)2} binuclear SBUs based 6-connected (4(4)·6(11))-6T8 framework. In addition, the magnetic property of complexes , and the luminescence properties of complexes , were investigated.

摘要

在溶剂热条件下,以两种双(咪唑)桥连配体(bimb = 1,4 - 双(2 - 甲基咪唑 - 1 - 基甲基)苯,bibp = 4,4' - 双(咪唑 - 1 - 基)联苯)为原料,合成了四种新型配位聚合物,即[Co(H2O2abtc)(bibp)]n ()、{[Mn1.5(Oabtc)(H2O)2]·(H2bmib)0.5·H2O}n ()、{[Cd1.5(O2abtc)]·(H2bmib)0.5·2H2O}n ()和{[Cd(nip)(bibp)]·0.5H2O}n ()。3,3',5,5' - 偶氮苯四羧酸(H4abtc)的不稳定偶氮配体可被氧化,生成三种氧化衍生物H4Oabtc(一个N原子被氧化)、H4O2abtc(两个N原子被氧化)和H2nip(一个H4abtc被氧化为两个5 - 硝基间苯二甲酸)。通过单晶X射线衍射确定了它们的结构,并通过元素分析、红外光谱、粉末X射线衍射(PXRD)和热重(TG)分析进行了进一步表征。配合物基于4 - 连接(4(4)·6(2))- sql层呈现出有趣的2D + 2D → 3D平行缠结网络。配合物被发现是基于{Mn3(COO)6}三核SBU的二维(3,6)- 连接(4(3))2(4(6)·6(6)·8(3)) - kgd层。而配合物展示出基于{Cd3(COO)8}三核SBU的三维(4,8)- 连接(4(6))2(4(12)·6(12)·8(4)) - flu网络。配合物可被视为基于{Cd2(COO)2}双核SBU的6 - 连接(4(4)·6(11)) - 6T8框架。此外,研究了配合物的磁性以及配合物的发光性质。

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