【作者】 赵小亮；

【导师】 孙道峰；

【作者基本信息】 山东大学 ， 无机化学， 2012， 博士

【摘要】 由于金属-有机配合物在光学、磁性、催化、气体吸附和分离等方面具有优良的性能,所以设计合成功能金属-有机配合物已成为当今配位化学的研究热点之一,亦是难点之一。与传统无机分子筛不同,金属-有机配合物具有结构和性质的可调控性。在此类配合物的组装中,不仅溶剂、温度、pH值等诸多外在影响因素,而且配体自身构型和金属离子或者金属簇基元的配位模式对金属-有机配合物的最终结构有至关重要的作用。作为重要构筑基元之一的有机配体可以预先设计并合成,使与具有不同配位模式的的金属离子或者离子簇基元相互连接,实现金属-有机配合物的定向组装。因此如何设计合成功能有机连接体,有目的的组装具有特定结构的金属-有机配合物对功能配位化合物领域的发展具有重要意义。在过去的几十年中,共平面的芳香族羧酸类配体因其具有较强的配位能力以及多样化的配位方式被广泛应用于金属-有机配合物的组装中。由于配体本身的构型对最终的金属-有机配合物结构有着重要的影响,所以本论文设计合成了一系列非同平面大骨架芳香性多羧酸类配体(H3L1,H6L2,H4L3,H4L4,H4L5,H6L6,H6L7,H6L8,H4L9),通过配位键与金属Zn2+、Cd2+和Cu2+组装合成出16个新颖的配位化合物,并通过X-射线单晶衍射、元素分析、热重分析、X射线粉末衍射、荧光分析、圆二色分析和气体吸附测试对它们进行结构表征和性能测试。本论文的主要内容如下：一、利用具有甲基位阻效应的非共平面的芳香性三羧酸配体H3L1与Zn2+构筑配合物1,2和3,进过结构分析发现它们是因为层间作用力不同而引起的二维层间的堆叠方式不同进而形成的超分子异构体,同时发现配合物2是手性结构,通过用手性小分子诱导得到单一手性的配合物2；二、由两种吡啶类配体作为第二配体连接平行的双层相互穿插形成的三维微孔金属-有机配合物4-5,对其进行气体吸附测试和比较发现第二配体的长度影响配合物的孔径大小进而影响气体吸附性能；三、由刚性的大骨架芳香性多酸配体H6L2与Zn2+自组装构筑的含有笼状的金属-有机配合物6,并对其结构和拓扑进行解析。由刚性的大骨架芳香性多酸配体H4L3和H4L4与Zn2+和Cu2+自组装构筑的微孔金属-有机配合物7-9,并对其结构进行解析；四、含硅的芳香性四羧酸配体H4L5与Cd2+构筑配合物10和11,分析了因溶剂不同得到(4,4)连接的配合物10和(4,8)连接的flu拓扑结构的三维微孔配合物11。含硅大骨架多酸配体H6L6,H6L7和H6L8与Cu2+构筑的笼状配合物12-14,经过晶体结构和拓扑分析发现他们具有相同的结构,即(3,24)连接的rht拓扑结构。重点比较了因中心原子Si上修饰不同的基团对最终配合物12,13和14气体吸附的影响；五、开创了一种新型的组装配合物的方法,即相转移催化剂参与的室温双相合成法,为配合物的合成提供新的途径,并用此方法合成了非穿插的一维金属-有机纳米管状配合物15和存在一维水带的一维链状配合物16。更多还原

【Abstract】 Nowdays the design and synthesis of new functional metal-organic coordination complexes is an active and difficult research filed for their potential applications in photoelectricity, magnetism, catalysis, gas adsorption, separation and so on. Metal-organic coordination complexes are adjustable comparing with traditional zeolites. Besides the external conditions such as the solvent, temperature, pH etc., the ligand conformation and the coordination geometries of metal ions or metal clusters have a crucial impact on the final structure of MOFs. The semi-direactional synthesis of MOFs can be realized through the connecting the metal ions or metal cluster and the ligand as the spacer which can be pre-designed. It is important to control the conditions for obtaining the desired MOFs.In recent years, planar aromatic carboxylate ligands have been widely researched due to their varieties of coordination modes and strong coordination ability. Based on the influence of the ligand,.we designed and synthesized a series of nonplanar aromatic multi-carboxylate ligands with a big rigid structure (H3L1, H6L2, H4L3, H4L4, H4L5, H6L6, H6L7, H6L8, H4L9).16novel MOFs were obtained through the assembly reactions between the synthesized ligands and Zn2+, Cd2+, Cu2+. All complexes have been characterized by single-crystal X-ray diffraction, elemental analyses, thermal analysis, XRPD analysis, fluorescence spectroscopy, circular dichrosim and gas adsorption. The contents of this dissertation are as follows:1. H3L1is nonplanar for the three methyls of the central benzene ring. Complexes1,2, and3were obtained by the assembly of H3L1and Zn2+. These three complexes are supramolecular isomerisms driven by CH---π interactions among the two dimensional honeycomb layers, while complexe2is homochiral crystallization from an achiral ligand through chiral inducement.2. Two porous MOFs (4,5) have been synthesized by polycatenation between the bilayers which are connected by two different pyridine ligands. By comparing the adsorption results, the length of the second ligand affects the size of pores of MOFs. 3. Complexes6-9is the assembly of metal ions and ligands (H6L2, H4L3, H4L4) which are big rigid aromatic structures. Their structures and topologies have been described and analyzed. They are all porous MOFs with polyhedrons or cages.4. Four different silicon-based ligand have been designed and synthesized. We synthesize and characterize two Cd(Ⅱ)-H4L5, Cu-H6L6, Cu-H6L7and Cu-H6L8coordination polymers. The solvent system plays an important role in modulating the final structures. Complexe10and11present2D (4,4) net and (4,8)-connected3D porous framework with flu topology. Complexes12,13and14show the same (3,24)-connected3D porous framework with rht topology. We mainly invesitigate the effect of the modified groups on the central silicon atom on the gas adsorption among the complexes12-14with the same structure.5. A novel Metal-organic nanotube (15) and a1D coordination polymer (16) with large water clusters are obtained and characterized via a new synthetic approach: phase-transfer catalyst supported, room-temperature biphasic synthesis. The new nanotubular material (15) is non-interpenetrating because of the large template of [Cu(py)4Cl·Cl] and the steric hindrance effect of the methyl groups of H4L9. It is interesting to observe that1D novel water tape with an8-membered ring as the basic unit reside in complexe16.更多还原