金属-有机框架论文：由多齿四氮唑衍生物配体构筑的多孔金属—有机骨架的合成,结构及性质研究.doc

金属-有机框架论文：由多齿四氮唑衍生物配体构筑的多孔金属有机骨架的合成，结构及性质研究【中文摘要】金属-有机骨架化合物因其独特的结构可调控、特殊的拓扑结构以及在气体存储及分离、荧光探针、生物载药等领域的潜在应用引起了人们的广泛关注。现今四氮唑基团因其具有多齿配位模式,可形成结构多样及特殊的结构正被越来越多的人用于金属-有机骨架化合物的构筑。本论文利用新型的四氮唑衍生物配体1,3,5-苯三四氮唑(1,3,5-benzenetristertrazolate, BTT3-)与不同金属在不同条件下得到了6种配合物。研究表明:在合成金属-有机骨架材料过程中,金属盐与有机配体的配比是至关重要的因素。此外,我们还研究了部分配合物的磁性和N2吸附性质。具体内容如下:1、利用1,3,5-苯三四氮唑与金属锌和锰盐在水热条件下合成了两种互为同构的化合物, （1）, （2）。这两种化合物都是基于四核由3-OH和金属原子构成的金属氧簇的三维网络结构。值得关注的是,在结构中含有四核金属氧簇由金属原子连接而成的二维层状结构,而这些二维层状结构式相互平行的,并由BTT配体柱撑形成三维网络结构。我们还研究了化合物1的固态荧光性质和化合物2的磁性。2、利用非手性的1,3,5-苯三四氮唑配体与过渡金属钴在溶剂热条件下得到了具有手性的三维孔道化合物, 5CH3OH6DMA （3）。化合物3具有（10,3）-a网络拓扑结构包含大的螺旋孔道17.43 ,且含有高达79%的有效溶剂体积。我们还研究了该化合物的磁性和N2吸附性质。3、利用1,3,5-苯三四氮唑配体和过渡金属Zn在溶剂热条件下,得到三个化合物:2DMA （4）, CH3OH3DMA （5）, CH3OH5DMA6H2O （6）。化合物4是基于（3,6）-连接的具有一维菱形孔道的三维微孔网络结构。化合物5是基于（4,4）-连接的具有单臂纳米管孔道的三维网络结构。化合物6是基于（3,6）-连接的具有哑铃型的介孔笼的三维网络结构。值得注意的是,这三种化合物是在相同溶剂环境下以不同金属盐和BTT配体配体得到的。虽然化合物4和6的网络拓扑连接是一样的,但由于BTT配体的配位模式不同,而导致它们的结果也大不相同。【英文摘要】Metalorganic frameworks （MOFs） has recently attracted considerable interest, owing to their versatile framework topologies as well as their potential applications as functional materials in molecular magnetism, catalysis, gas sorption, fluorescent sensing, and optoelectronic devices. The tetrazolyl functional group has found a wide range of applications in coordination chemistry as ligands, in pharmaceuticals as a metabolically stable surrogate for a carboxylic acid group, in photography and information recording systems, and in materials science as high-density energy materials. In this paper, we using 1,3,5-benzenetristertrazolate and different metal ions in different conditions abtain six metal-organic frameworks. According to investigation, It is found that it is crucial for syntheses of metal-organic frameworks to control the ratio of metal ions and BTT ligands. Furthermore, magnetic properties and N2 adsorption have also been studied. The main contents are summarized as below:1. We have successfully synthesized two novel isostructural compounds by combining polytetrazolate rigid ligand. The3-OH group linked MII （Zn and Mn） atoms to form interesting 2D layers structure and the BTT bridged adjacent layers to give a 3D network with tetranuclear metal-oxygen clusters and 16-membered metallocycles. The most intriguing feature is that metal atoms act as linkers to bridge the metal-oxygen clusters. In addition, the photoluminescent property of 1 was also investigated, the maximum emission of compound 1 exhibits a great red-shift （about 67 nm） in comparison with the free ligands. The magnetic property of 2 studied indicates that antiferromagnetic interactions exist between neighbouring Mn （II） ions.2. We have successfully constructed a 3D chiral microporous （10,3）-a topology metalorganic framework based on binuclear cobalt units and H3BTT ligands. Noteworthily, complex 3 exhibits large chiral channels of 17.43 and a high solvent-accessible volume （calculated 79%）. In addition, the gas adsorption experiments of N2 and magnetic property of 3 have been investigated.3. Three new compounds, Zn（HBTT）2DMA （4）, Zn2（BTT）（OH）（H2O）CH3OH3DMA （5）, Zn（DMA）6Zn6（HBTT）6CH3OH5DMA6H2O （6）, have been solvet synthesized on the basis of 1,3,5-benzenetristertrazolate and metal zinc ions. Compound 4 displays a 3D noninterpenetrating with 1D rhombus chnnels based on （3,6）-connected net. Compound 5 displays a 3D noninterpenetrating with carbon nanotubes sructure based on （4,4）-connected net. Compound 6 displays a 3D noninterpenetrating net with dumbbell-like mesoporous cages based on （3,6）-connected net.【关键词】金属-有机框架 拓扑结构 磁性 N2吸附【备注】索购全文在线加我：13.993.8848 同时提供论文辅导写作和学术期刊论文发表服务 本文为学术文献总库合作提供，无涉版权。作者如有异议请与总库或学校联系。【英文关键词】Metalorganic frameworks Topology Structure Magnetic property N2 absorption【目录】由多齿四氮唑衍生物配体构筑的多孔金属有机骨架的合成，结构及性质研究摘要4-5Abstract5第一章 引言8-261.1 金属-有机骨架化合物的发展8-91.2 金属有机骨架材料的应用研究9-211.2.1 气体存储9-121.2.2 磁性材料12-131.2.3 催化材料13-151.2.4 光学材料15-171.2.5 生物载药材料17-211.3 选题依据和目的211.4 实验试剂和测试手段21-22参考文献22-26第二章 水热合成由刚性四氮唑衍生物配体构筑的基于四核金属氧簇的配位聚合物的合成、结构与性质研究26-372.1 引言262.2 配合物的合成与表征26-272.2.1 化合物的合成26-272.3 结果与讨论27-322.3.1 晶体结构的测定和晶体学数据27-292.3.2 结构分析29-322.3.3 讨论322.4 性质研究32-342.4.1 PXRD 性质32-332.4.2 荧光性质332.4.3 热重性质33-342.4.4 磁性342.5 结论34-35参考文献35-37第三章 基于(10,3)-a 拓扑的三维手性微孔金属-有机骨架化合物37-503.1 引言37-383.2 化合物的合成383.3 结果与讨论38-433.3.1 晶体结构的测定和晶体学数据38-393.3.2 结构分析39-423.3.3 讨论42-433.4 性质研究43-463.4.1 PXRD 性质43-443.4.2 热重性质443.4.3 N_2 吸附性质44-453.4.4 磁学性质45-463.5 结论46-47参考文献