【作者】 张鹏；

【导师】 李东升；

【作者基本信息】 延安大学 ， 分析化学， 2011， 硕士

【摘要】 随着分析科学与化学的其它分支学科,以及与材料、生命、能源环境等学科的交叉、融合,现代分析测试技术的表证功能备受研究者关注,并已应用到化学与材料研究的诸多领域。金属有机配合材料（MOFs）不仅兼有无机材料和有机材料的优点,而且具有可调控性与多孔性等特点,赋予其迥别于纯无机或有机固体的优势和发展空间,是目前化学、材料、医药等学科研究的交叉前沿之一。如何在分子水平探索分子间相互作用的本质,进而实现对其结构乃至物性的调控,对于深入研究结构与物性的关联,并最终实现“设计”合成和工业应用具有重要的意义。本论文选用三种不同类型的配体与过渡金属离子反应合成了12例具有新颖结构的MOFs材料,即:1.以柔性的长链V型配体为结构基块,不同的过渡金属离子为中心,合成了4例MOFs （1-4）。[Co（Hoba）₂（H₂O）₂] （1）,[Co（oba）（bip）] （2）,{[Ni（oba）（btp）]·（H₂O）_0.5} n （3）,{[Cu（oba）（btp）]·（H₂O）_0.5}_n （4）（其中H₂oba = 4,4’-氧双二苯甲酸）;2.在溶剂热条件下,选用合理的有机配体和d10金属离子,辅以不同的N-给体共配,合成了3例超分子网络（5-7）。{[Cd（pid）（H₂O）]·H₂O}_n （5）,[Zn（pid）（bpp）（H₂O）]_n （6）,{[Zn（pid）（2,2’-bipy）（H₂O）]·2H₂O}_n （7）（其中H₂pid = N-苯基亚胺二乙酸）;3.采用多功能建筑块和d10金属离子,合成了5例MOFs材料（8-12）。[NaCd（2-EtIMDC）]n （8） , [Cd（2-EtIMDC）₂（bix）_0.5（H₂O）]_n （9） ,[Cd₂（2-EtIMDC）₂（dpe）（H₂O）]_n （10） , [Cd（2-EtIMDC）（bpp）]_n （11） ,{[Zn（2-EtIMDC）（bpp）_0.5（H₂O）]·H₂O}_n （12）（其中2-EtIMDC = 2-乙基-4,5-咪唑二羧酸）。以这些晶态材料为研究对象,运用X-射线单晶衍射分析、元素分析、红外光谱、热重分析、荧光光谱、磁性测试等现代分析表征技术,对其结构、拓扑类型和荧光与磁学性能进行了表证研究,在此基础上总结了上述材料的合成规律,归纳了所属网络的拓扑类型,分析了分子间作用力、配体的几何构型、辅助配体等因素对这些晶态材料结构与性能的影响规律,探索了拓扑类型、结构与性能间的内在关系,获得了一些规律结论。更多还原

【Abstract】 With the promoting intersection and merging of analytical chemistry with subdiscipline of Chemistry, materials science, biological science and energy and environmental science, available modern testing means particularly important to the analysis of functional materials. In this respect, one of current hot spots is Metal–Organic Frameworks （MOFs）. It offers a unique platform for the development of solidstate materials as they have a degree of structural predicatability and the possibility of permanent porosity, which leads to features not observed for traditional inorganic or organic complexes.How to explore the intermolemolecular interactions and its nature at the molecular level, further achieve controllable probing into the relationship between the structure and functions and ultimately realize the“design”synthesis and industrial applications. In this contribution, firstly, aborative design and select the organic tectons, and mainly investigate the regularity of assembly and mechanism of the coordination materials, synthesize 12 MOFs. The study on synthetic conditions and rules for these novels MOFs, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out.Twelve new MOFs have been synthesized on the basis of hydrothermal technique and solvent synthesis methods, and these materials were characterized through X-ray single crystal diffraction analysis, elemental analysis, fourier transform infrared spectra technology, thermal analysis technology. The Furthermore, we focus on the analysis and study of structural features、thermal stabilities、magnetic properties and fluorescent activity of aforementioned materials also have been studied.1. Introducing the principle of structural block-oriented, different metal ions as the center, 4 MOFs （1-4） were synthesized, including two 2-D layered structures and two 3-fold interpenetrated CdSO₄ net.2. Three 3-D supramolecular lattices （5-7） with hetero-chiral helical chain have been solvothermally synthesized. Compound 5 presents 2-D network with （4·8²） topology based on 4-connected nodes.3. Using the heterocyclic carboxylic acids as building blocks, 5 MOFs （8-12）were synthesized, and systemically investigated the assembly regularities of entanglement networks using in situ square-MBBs （molecular building blocks） as the molecular tectons. Compound 9 exhibits the twofold （2D→2D） entangled features with interlaced in a highly rare parallel fashion. Compound 10 represents a new 3,4-connected self-penetrating network topology, in which each 2-D sheet passes through an inclined one at angle of 78.94?. 8, 11 and 12 take different 1-D helical chains structure.更多还原