Design, Synthesis And Catalytic Applications Of Metalloporphyrinic Frameworks Based On5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin

Metalloporphyrinic Frameworks (MPFs), constructed from metalloporphyrinic building blocks which possess unique biological and chemical properties, are emerging as very promising functional materials for gas adsorption, luminescence and catalysis because of their permament porosities and the unique properties provided by the functional porphyrinic building blocks. In the field of MPFs, the catalytic applications can be achieved through the rational design and synthesis of porous MPFs with nano-sized channels (cavities) by using metalloporphyrinic building blocks. The catalytic activities of MPFs will be specifically studied according to the identities of metalloporphyrins and the structural characteristics of MPFs.Our goal is to construct a series of MPFs using metalloporphyrinic building blocks and study their catalytic activites. In this thesis, seven MPFs have been synthesized through the self-assemble reaction of metal-5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-OCPP. M=NiⅡ, MnⅢCl) and inorganic metal nodes, including MnⅡ, CdⅡ, ZnⅡ and CuⅡ by tuning the crystal growth conditions such as reaction temperature, pH, solvent, and the loading of metal ions, etc. These MPFs have been throughly characterized by single crystal X-ray diffraction, powder X-Ray diffraction, IR, TG and elemental analysis. The permanent porosities of these MPFs were studied by gas, solvent or dye sorptions. According to their structural characters, porphyrin metals and metal nodes, the catalytic activities of these MPFs were studied in the alkylbenzene oxidation (MPF-1), olefin epoxidation (MPF-5) and Cross-Dehydrogenative Coupling reaction (MPF-6and7), respectively. The relationship between reaction factors and the catalytic activities were also studied. The studies on the systematically tuning the MPFs’ structures and catalytic activities will provide valuable information for the development of new MPFs materials in the future.