Fan Liming, Fan Weiliu, Li Bin, Liu Xinzheng, Zhao Xian, Zhang Xiutang
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.
Dalton Trans. 2015 Feb 7;44(5):2380-9. doi: 10.1039/c4dt03076a.
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.
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。