| In the past two decades, metal-organic frameworks (MOFs), a promising class of coordination polymer materials, have been developed and applied as gas separation/storage materials, drug delivery vehicles, light-harvesting material, and catalysts. MOF materials are attractive candidates for the listed applications due to their permanent microporosity and tunable nature. This dissertation describes the design, synthesis, and application of MOF catalyst materials that incorporate N-Heterocyclic carbene (NHC) and hydrogen-bond donor (HBD) catalysts. Libraries of novel MOF struts that emulate well-precedented homogeneous catalysts and act as NHC and HBD catalysts have been synthesized. These struts have been used to synthesize a series of MOF catalyst materials. Among the MOFs synthesized is the first microporous MOF to incorporate azolium salts, a series of unusual zwitterionic MOFs, analogs of known MOF materials, and novel MOF that incorporate HBD catalysts.;Azolium MOFs CuMAFc and NU-303 have been applied as gas storage and gas separation materials respectively. MOFs NU-501-504 demonstrate catenation control by rational ligand design, and NU-601 was shown to be a novel heterogeneous HBD catalyst that is more reactive than a related homogeneous catalyst, size selective, robust, and reusable. |
