Design, Synthesis And Characterization Of Novel Metal-organic Frameworks

As a novel porous material, metal-organic Frameworks possess not only porous phase similar to inorganic zeolites but also better performance in sorption and separation of small molecular than traditional zeolites. In addition, functional and rational design of the length and geometry of organic molecular ligand make such metal-organic frameworks display the especial flexible tailoring, various topologies, molecularre-cognization, catalysis along with optics, electrics, magnetism and enantioselectiveseparation. So, these materials have great application in many fields.According to synthesis, structures and multifunctional properties of MOFs, we have focused our study on the influence in the synthesis, topology structure and character of multifunction, especially on the coordination capability of the different organic ligands and metal center to control the MOFs structure. Meanwhile, we also search the suited condition for special second building units (SBU), these works will supply useful information for synthesise of metal-organic framework. In this dissertation, we have prepared 14 new MOFs by using different organic ligands and metals. We also analyzed their topology structures as well as explored their multifunctional properties. These results will be introduced from the following issues:(1) Mixtures which contained target product are often obetained from chemistry industry. These compounds can be separated easily if the physical or chemical character of them are largely different, otherwise, that is hardly to be done. So if we want to get the pure target product in the fields of chemical industry, medicine and food, we should separate the mixture efficiently. On the other side, facing the flinty problem of the energy and environment, we should make use of raw material efficiently.Xylenes are valuable to used as the raw material in the manufacture, so enhance the separation impact is very important. We use ligand OBA and In(NO3)3 to synthesize a novel MOF [In(OH)(OBA)]?DMF (1). According to the simulation of this MOF ,we found that the channel along the [001] direction indicated that 1-D dumbbell-like channel only allows simple 1-substituted or p-substituted Aromatics to go though. Result of liquid sorption experiment implied that this compound has potential capability for separating pX from xylenes.(2) Although the mechanism for synthesis of metal-organic framework has not been revealed yet, but we found that some second building unit(SUB) often can be got at the certain reaction conditions, paddle-wheel(Cu2/Zn2(COO)4), Zn4O(COO)6. Base on these research, we can synthesize the MOF materials in the certain way. The analyse of the MOFs'topology structure is of great significance in designing and preparation mOFs with desired structure. We successfully synthesized four metal-organic framework with three cores SBU at the similar conditions by using diffusing method. In addition, four MOFs with familiar topology structures also have been synthesized. We hope that these experiment will offer useful information for synthesis of metal-organic framework in future.(3) Compared with the inorganic zeolites, metal-organic frameworks are a new class of porous materials which were assembled by organic and inorganic second building units (SBU). These organic ligands make the framework tailored and multi-functional. Kitagawa group and Kim group have been done numbers of work on synthesizing 3D metal-organic framework according to'Pillared'method, they also have done lots of works on adjusting the size of channels by changing the length of ligands. In addition, geometric of the ligand is very important for the stability of metal-organic framework. So, in designing and synthesizing MOFs, we should not only choose rational metal to build the desired SUBs by topology, but also consider that stability and properties of the target metal-organic framework which are under the influence of the ligands.By using adamantane as the initial raw material, we have synthesized a novel organic molecular: 1,3,5,7-tetrazole-adamantane. And we get two novel metal-organic frameworks with CaF2 network by using the ligand above. we also synthesized three compounds by using OBA and 4,4'-bpy ligands. At the same time, we studied on the infunce of the solvent system for synthesizing the metal-organic framework.