基于一个四羧酸配体的镧系金属-有机框架材料及其对有机小分子的检测  

Two Lanthanide Metal-Organic-Frameworks Based on a Tetra-carboxylate Ligand for Sensing of Small Organic Molecules

作　　者：林建军 刘珍[1] 吕灵芝 冯云龙[1] 

机构地区：[1]浙江师范大学化学与生命科学学院,浙江省固体表面反应重点实验室,金华321004

出　　处：《无机化学学报》2018年第2期230-236,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(N0.21173197)资助项目.

摘　　要：以四羧酸3,5-双间苯二甲酸-1,2,4-三氮唑(H4L)为配体,与镧系金属Ln髥盐反应,自组装合成了2个具有三维孔洞结构的镧系金属-有机框架材料(Ln-MOFs):{[Ho_3L_2(H_2O)_6]OH·2DMF}_n(1),{[Tb_3L_2(H_2O)_6]OH·2DMF}_n(2)。单晶X射线衍射分析表明,1与2属于异质同构晶体,为单斜晶系C2/m空间群。3个LnⅢ离子通过8个羧基桥联形成三核[Ln3(COO)8]次级结构单元,晶体由[Ln3(COO)8]次级结构单元相互连接形成一维无机链,链与链之间通过配体L4-相连形成具有一维孔道的三维网络结构。有机小分子溶剂交换荧光研究表明,2在硝基苯溶剂中表现出荧光猝灭现象,Tb-MOF材料对硝基苯等爆炸物具有良好的荧光探测功能。5,5＇-（1H-1,2,4-triazole-1,4-diyl）diisophthalic acid （H4L） was used to synthesize two microporous three-dimension metal-organic-frameworks（MOFs） with lanthanide metal salts by intermolecular self-assembly：{[Ho3L2（H2O）6]OH·2DMF}n （1）, {[Tb3L2（H2O）6]OH·2DMF}n （2）. Single-crystal X-ray diffraction revealed the Ln-MOFs are isomorphous and belong to monoclinic C2/m space group. Three Ln（Ⅲ） ions are connected through eight carboxylic groups to form a trinuclear[Ln3（COO）8] SBU. The SBU polyhedrons share edges with each other generating a 1D inorganic chain, and the chains are further connected by the L4- ligands to construct a 3D framework. The luminescence intensity of 2 can be modulated by organic small molecules, and 2 exhibited the significant quenching in nitrobenzene, which indicates that 2 is potential luminescent sensing material for nitro explosives.

关 键 词：3 5-双间苯二甲酸-1 2 4-三氮唑 稀土 金属-有机框架材料 晶体结构 荧光性质 

分 类 号：O614.343[理学—无机化学] O614.341[理学—化学]