| With the advent of new analytical technologies and a firm grasp on the fundamentals of chemical reactivity, the area of coordination-driven self-assembly has grown significantly over the last number of years. This field can be roughly divided into two subcategories: the solution and solid-state based area of discrete molecular architecture (DMA) and the more materials-oriented discipline of coordination polymers and network solids. The former deals exclusively with single molecules that form in solution before crystallizing out, while the latter is focused on infinite systems in the solid-state. Both hope to present chemists with large and well-defined, novel compounds that may have several potential applications and can be synthesized with relative ease and predictability.; In this dissertation, a number of new coordination polymers based on transition metal(hexafluoroacetylacetonate)2 complexes and a variety of weak backbone interactions, such as pyridine-metal, pyridine(N -oxide)-metal, and hydrogen-bonding, are presented. These species allow for a greater understanding of the particular bonding and chemistry of the metal-ligand combinations themselves, as well as insights into more general structural phenomena.; Additionally, the reactions of manganese(hexafluoroacetylacetonate) 2 with a flexible ditopic, dipyridine donor unit are explored. This system can be transformed from homochiral helices to syndiotactic wedge-shaped polymers to discrete macrocycles by simply changing the organic template involved in the reaction. In so doing, it may serve as a potential first step in bridging the heretofore disparate fields of DMA and coordination polymers. The inter- and intramolecular interactions responsible for the differing structures are also investigated, lending a possible crystal engineering aspect to the studies as well.; Finally, the concept of expanding both DMA and coordination helices to include not only covalently-defined motifs but also those based on conformationally-defined phenomena, such as the hindered rotation seen in the S-S bond of dithiodipyridine, is explored. In this section, the ∼90° dihedral angle of the ditopic, nucleophilic tecton leads to predictable structures in both subcategories of self-assembly. |
