Design and synthesis of crystalline and amorphous coordination materials

This dissertation is centered on two areas: (i) rational design and synthesis of robust porous metal-organic frameworks using well-defined building blocks and (ii) synthesis of crystalline and amorphous coordination polymers based upon traditional organic chemistry. For the rational design and synthesis, we demonstrated how to achieve maximum interpenetration by fine tuning the size of the organic spacer using the Secondary Building Units (SBUs) approach, and how to avoid interpenetration using almost the same size of organic spacer via a pillared-layer strategy. For synthesis based on organic chemistry, we have developed a complementary and alternative covalent-based synthetic strategy for the synthesis of new coordination compounds in an effort to incorporate a wider range of compounds in the family of coordination materials.We synthesized a 4-fold mixed parallel/diagonal interpenetrating cubic metal-organic framework using octahedral zinc carboxylate Zn4O(OOC-) 6 SBUs as nodes and a long and narrow organic ligand, 1,4-(4-carboxylic-phenyl) butadiyne, as linkers. Despite the maximum 4-fold interpenetration, it contains large void space and high specific surface area. We synthesized two pillared-layer metal-organic frameworks using infinite 2D tetragonal grid lattices and kagome lattices as Supramolecular Building Blocks (SBBs), respectively. The interpenetration was forbidden in these two frameworks by judicious choice of impenetrable 2D SBBs. Both pillared-layered frameworks possess unprecedented levels of porosity. The pillared-layer architecture paradigm we demonstrated in this dissertation points to a design strategy for the synthesis of large microporous, even mesoporous metal organic frameworks (MOFs).We modified discrete SBUs, synthesized coordination polymer gels and crystalline coordination polymers by using common organic coupling reactions including Huisgen 1,3-dipolar cycloaddition and homo-alkyne coupling reactions. We modified coordination nanospheres with long hydrocarbon chains by esterification reactions. The new covalent-based synthetic method can provide a wider range of coordination materials.