Crystal Engineering of Metal-Carboxylate Based Coordination Polymers

This dissertation endeavors to delineate practical paradigms for crystal engineering based upon the understanding of supramolecular chemistry and self-assembly, i.e. the design and synthesis of novel functional crystalline materials. Two basic metal-organic building units, Zn(RCO2)2(py)2 and (L2)M2(RCO2)4 (M = Zn, Cu), as well as nano-scaled secondary building units (nSBUs) that are constructed from Cu2(RCO2)4 are researched and discussed. Design strategies have been developed to propagate these metal-organic synthons into predictable coordination polymer networks. A series of crystal structures, as well as their syntheses and characterization, are presented. This work demonstrates that supramolecular structures can be designed from pre-selected molecular precursors with the consideration of chemical functionalities and geometrical arrangements. The design strategy represents a practical paradigm for the construction of porous materials as well as interesting networks with special topologies. The modular nature of these metal-organic building units introduces a broad impact on the discovery of novel coordination compounds with potential useful properties