Synthetic development of crystalline porous materials for gas sorption based applications

Metal-organic frameworks (MOFs) have attracted considerable interest because of their intriguing structures and potential applications such as gas storage and separation. Currently, of particular importance is the design and synthesis of porous MOFs with novel composition and topology. The work presented in this dissertation is focused on the design and syntheses of two different kinds of novel porous MOFs and their potential application as gas storage materials.;First, we demonstrate a versatile synthetic method capable of generating a large family of novel 4-connected lithium imidazolate frameworks including ten two-dimensional and two silica-type three-dimensional frameworks. Lithium is the lightest metal and has the potential to produce attractive Li-OFs with low framework density that is desirable for enhancing gravimetric energy storage capacity of gas storage materials. We have developed a synthetic method based on the use of mixed charge-complementary ligands (L- and L0, L = ligand) designed to prevent excessive negative charges surrounding Li sites.;The second aspect of this work is focused on the design and syntheses of porous indium-organic frameworks. Interestingly, in this work, both {In(O 2CR)4} and {In3(O)(O2CR)6(H 2O)3} building blocks are integrated into the same architecture to give rise to a few unprecedented cage-within-cage-based highly porous indium-organic frameworks. These unique indium-organic frameworks not only exhibit high hydrothermal, thermal, and photochemical stability but also attractive structural features contributing to a very high CO2 uptake capacity of up to 119.8L/L at 273 K and 1 atm.