Designed Synthesis Of Functional Ligands Based Metal-Organic Frameworks And Catalytic Application

Metal-Organic Frameworks (MOFs) are a hot research topic of Coordination-Chemistry and Material-Chemistry. MOFs are playing very important roles in catalytic applications due to their unique pre- designability, post-decorationablity and convenient modification of cavity sizes and functional groups. Using pre-designed functional ligands as building blocks to construct MOFs containing functional groups is a main research method in this area. By detailed single crystal X-ray structure analysis, we can learn exactly how the MOFs to act during the catalytic process which can be subsequently used to direct a specific catalytic experiment.In this thesis, we have synthesized eight metalloporphyrins based on meso-tetra(4-carboxyphenyl)porphyrin (TCPP), including H4-TCPP, H4-Niâ…¡TCPP, H4-Cuâ…¡TCPP, H4-Ruâ…¢ClTCPP, H4-Pd"TCPP, H4-Mnâ…¢ClTCPP, H4-Feâ…¢ClTCPP, H4-Vâ…£OTCPP, and one metalloporphyrin based on meso-tetra(4-(4-pyridyl)porphyrin) which is Snlv(OH)2TPyP, and one optical active ligand which is (E)-5-(2-(pyridin-4-yl)vinyl)isophthalic acid (H2pyvia). We have used these ligands to ract with metal ions including Znâ…¡, Mnâ…¡, Cdâ…¡, Pbâ…¡to generate eighteen new compounds either in a direct way or by adding assistant ligand (DPNI). By tuning crystal growth conditions of reaction temperature, solvent etc., we have synthesized eighteen compounds, of which most of them are micro- or nano-porous. We have used single crystal X-ray diffraction, powder X-Ray diffraction, IR, thermogravimetric analysis (TG) to characterize these compounds. By analyzing the differences of the crystal structural frameworks and the functional groups, four of them were employed as efficient catalysts for the catalytic Heck Coupling, Selective Oxidation and Photo-degradation reactions. Detailed experiments were carried out to figure out the relationships between the framework structures and catalytic activities.