Zn(Ⅱ)与5-氨基四氮唑和1,4-对苯二甲酸配位聚合物的溶剂可控合成

Diverse Structures of Two Zn(Ⅱ) Coordination Polymers with 5-Amino-tetrazolate and 1,4-Benzenedicarboxylate Tuned by Solvent System

以5-氨基四氮唑(HATz)、1,4-对苯二甲酸(H2BDC)和Zn(NO3)2为反应物,在水热条件下得到了1个二维层结构的Zn(Ⅱ)配位聚合物{[Zn2(ATz)2(BDC)(H2O)2]·H2O}n(1),而在N,N'-二甲基甲酰胺(DMF)溶剂热条件下得到了1个三维结构的Zn(Ⅱ)配位聚合物{[Zn2(ATz)2(BDC)(DMF)2]}n(2).通过元素分析、红外光谱、单晶X射线衍射和粉末X射线衍射等对它们的组成和结构进行了表征.单晶结构分析结果表明,配合物1是以Zn(Ⅱ)离子作连接点、μ2-ATz-和μ2-BDC2-作连接子形成的3-连接(6,3)蜂窝型二维层结构,二维层之间再通过氢键作用形成三维超分子结构.配合物2是以两羧基桥连的双核Zn(Ⅱ)单元[Zn2(CO)2]作连接点、μ2-ATz-和μ4-BDC2-作连接子形成的6-连接简单立方格子的三维金属-有机框架结构.室温固体荧光实验表明,在350 nm的光激发下,配合物1和2分别在451和466 nm处出现强烈的荧光发射.

The hydrothermal reaction of 5-amino-tetrazole （HATz） and 1,4-benzenedicarboxylic acid （ H2 BDC） with Zn （ NO3 ）2 gave a new coordination polymer { [ Zn2 （ ATz）2 （ BDC ） （ H2 O） 2 ] H20 }, （ 1 ）, and when this reaction was carried out under N,N＇-dimethylformamide（DMF） solvothermal condition, another new coordination polymer { [ Zn2 （ ATz ）2 （ BDC ） （ DMF）2 ]/, （ 2 ） was obtained. Complexes 1 and 2 were characterized by elemental analyses, infrared spectroscopy, single-crystal X-ray diffraction, and powder X-ray diffraction. Complex 1 exhibits a 2D 3-connected（6,3） honeycomb（hcb） network with the Zn（ 11 ） ions as 3-connected nodes, and the/x2-ATz- and/x2-BDC2- ligands as linkers, and then strong hydrogen bonding interactions extend the 2D layers into 3D supramolecular framework. While, complex 2 possesses a 3D 6-connected primitive cubic（pcu） metal-organic framework with the binuclear Zn（ I1 ） units [Zn2（ CO）2 ] as 6-connected nodes, and the/x2-ATz- and g4-BDC2- ligands as linkers. Furthermore, their thermal stabilities and photoluminescence at room temperature in solid state were also investigated.