Design, synthesis and control of topology and properties of zeolitic imidazolate frameworks and metal-organic frameworks based on pyrazolate

The subject of this dissertation focuses on the design, synthesis and control of the properties for zeolitic imidazolate frameworks and metal-organic frameworks.; The goal is accomplished by adapting imidazolate and pyrazolate as linkers of frameworks, by developing effective structural directing agents (SDAs) and/or functionalizing imidazolate and by introducing in-situ ligand generation. Thirteen new compounds are synthesized with imidazolate or pyrazolate and Zn, Cu, and Co.; Zeolitic imidazolate frameworks (ZIFs) are composed of imidazolates and tetrahedral metal ions. Due to the bridging angle of imidazolate, ZIFs have the same topologies as zeolites. ZIF-1 (crb), ZIF-4 (dft), ZIF-7, -8, -9, -108 (sod), ZIF-10 (mer) and ZIF-11, -12 (rho) are synthesized and non-zeolitic topology ZIF-3 (cag) is synthesized. ZIFs shows higher thermal stability and chemical stability than metal-organic frameworks (MOFs) because of strong metal-nitrogen bonds and these are very important for the application.; MOF-324 and MOF-325 are synthesized with pyrazole carboxylate (PyC) and Zn or Cu. Because of two different linking moieties and the short length of PyC, MOF-324 and MOF-325 yield various pore sizes. The pore size of MOF-324 is on the border line of ultramicroporous materials. The pore size of MOF-325 is on the borderr line of mesoporous materials. Producing different pore sizes is characteristic of PyC.; MOF-326 is synthesized with pyrazabole dicarboxylic acid (PzDC) and Zn. PzDC has a partial charge and the effect of charge in hydrogen adsorption is investigated. Partial charge in PzDC shows weak interaction to hydrogen molecules as determined by calculating the heat of adsorption.