【作者】 谷献模；

【导师】 许宪祝；

【作者基本信息】 哈尔滨工业大学 ， 无机化学， 2010， 硕士

【摘要】 本文详细地阐述了含N、O配体和过渡金属组成的MOFs的合成条件和方法、结构特点、热稳定性及荧光性能。主要使用芳香多羧酸和氮杂环配体（即均苯三甲酸（H₃btc）、间苯二甲酸（H2ipa）、均苯四甲酸、N, N-二（2-吡啶）均苯四甲酸酰亚胺（ppt）,2, 4, 6 -三（4-吡啶）-1, 3, 5-三嗪（tpt）等）作为O、N源,通过溶剂热法,与过渡金属（Ni, Mn, Cd, Cu等）自组装成结构独特的MOFs化合物。成功合成两种有机配体:ppt和tpt。采用溶剂热法成功合成六个化合物: [Ni（H₂btc）（Hbtc）（tpt）（H₃O）]（1）,[Mn（tpt）（ipa）]（2）,[Ni(C₁₀H₂O₈)0.5（H₂O）2]·2H₂O（3）,[Cd(C₁₀H₂O₈)0.5（H₂O）3]（4） , [Cu（C₉H₄O₆）（H₂O）3]（5） , [Cd3（C9H3O6）2（H₂O）9]·2H₂O （6）,其中化合物1和化合物2中的有机配体是混合配体,而化合物3⁶的有机配体是单一配体。化合物1中存在η1和η2两种配位形式的均苯三甲酸,η2配位形式的均苯三甲酸将由Ni和tpt配位构筑的螺旋链连接成为二维层状结构,而η1配位的均苯三甲酸只起对螺旋链进行修饰作用;化合物2中,Mn原子将tpt配体连接成为zigzag链,同时,Mn原子与间苯二甲酸配位,形成了两条互相垂直的一维直链,因此,Mn原子将这三条沿着不同方向的一维链构成三维网络结构;化合物3是由Ni原子和均苯四甲酸配位形成的一个三维网络结构,其结构具有一维矩形孔道;化合物4中Cd原子与均苯四甲酸配位,最终形成一个具有两个不同尺寸孔穴的二维层状结构;化合物5中,Cu和均苯三甲酸配位形成一条zigzag链,又通过氢键的作用,最终形成一个三维的超分子网络结构;化合物6是一个由五配位和六配位的Cd原子交替与均苯三甲酸配位所构成的具有菱形孔穴的二维层状结构。此外,对六个化合物进行了热重分析及其荧光性能的研究,其中化合物2的热稳定性最好;化合物1,3,5在近紫外区有荧光,化合物2具有蓝色荧光,而化合物4和6具有紫色荧光。更多还原

【Abstract】 In the dissertation, we have intruduced in detail the conditions and methods of synthesis, structural features, thermal stability, fluorescent properties of MOFs based on N, O ligands and transition metals. We have prepared the MOFs with novel structures adopting solvothermal synthesis method using multi-carboxylic acid and heterocyclic aromatic ligands including trimesic acid （H3btc）, isophthalic acid（H2ipa）, pyromellitic acid N,N-di（2-pyridyl）-pyrrolo[3,4]isoindole-1,3,5,7-tetraone （ppt） and 2,4,6-tris（4-pyridyl）-1,3,5-triazine （tpt）, and transition metal composed of nickel, copper, manganese, cadmium and so on.We have successfully prepared two organic ligands: ppt and tpt. Furthermore, we have also successfully synthesized six MOFs: [Ni（H₂btc）（Hbtc）（tpt）（H3O）] （1）,[Mn（tpt）（ipa）] （2）,[Ni(C₁₀H₂O₈)0.5（H2O）2]·2H2O （3）,[Cd(C₁₀H₂O₈)0.5（H2O）3] （4）,[Cu（C₉H₄O₆）（H₂O）3] （5）,[Cd3（C₉H₃O₆）2（H2_O）9]·2H2O （6）. Among them, compounds 1 and 2 are comprised of mixed-ligands and compounds 3⁶ only include one type of ligand molecule. Especially, compound 1 displays a 2-D layered structure which is built byη2 coordination mode trimesc acid and helical chain formed by TPT ligands and Ni atoms, in 1, the trimesic acid adoptingη1 coordination mode also is found to modify the helical chain. Compound 2 displays a 3-D network structure with 1-D channel, which is comprised of three 1-D chains including one zigzag chain formed by Mn atoms and TPT ligands, and two mutually perpendicular 1-D straight chains built by Mn atoms and isophthalic acids along different directions. Compound 3 exhibits 3-D network structure possessing the 1-D rectangular channel, which is formed by Ni atoms and pyromellitic acids. Compound 4 with two different sizes caves possesses 2-D layered network structure is built from the transition metal Cd and pyromellitic acid. Compound 5 displays 3-D supramolecular network structure, which is formed by the 1-D zigzag chain built from Cu and trimesic acid via hydrogen bonds. Compound 6 exhibits 2-D layered network structure with diamond channel that is formed by the five-coordinated and six-coordinated Cd atoms and trimesic acid. We also carried out these six compounds thermogravimetric analyses and fluorescence properties, the stability of compound 2 with blue fluorescence is the best. Compounds 1, 3 and 5 exhibit the fluorescence in the near ultraviolet region, and compounds 4 and 6 exhibit purple fluorescence.更多还原