Hierarchical complexity in metal-organic materials: From layers to polyhedra to supermolecular building blocks

The design and synthesis of novel functional materials with fine-tunable physical and chemical properties has been an aspiration of materials scientists since at least Feynman\u27s famous speech There\u27s Plenty of Room at the Bottom which has fittingly been credited with ushering in the nanotechnology era. Crystal engineering, as the solid-state manifestation of supramolecular chemistry, is well positioned to make substantial contributions to this worthwhile endeavor. Within the realm of crystal engineering resides the subdiscipline of metal-organic materials (MOMs) which pertains most simplistically to the coordination bond and includes such objects as coordination polymers, metal-organic frameworks (MOFs), and discrete architectures, each of which share the common aspect that they are designed to be modular in nature. While metal-organic materials have been studied for quite some time, only recently have they enjoyed an explosion in significance and popularity, with much of this increased attention being attributed to two realizations; that this inherent modularity ultimately results in an almost overwhealming degree of diversity and subsequently, that this diversity can give rise to effective control of the properties of functional materials. At long last the goal of attaining fine-tunablity may be within our grasp. In addition to high levels of diversity, MOMs are also characterized by a broad range of complexity, both in their overall structures and in the nature of their constituents. From the simplest molecular polygons to extended 3-periodic frameworks of unprecedented topologies, MOMs have the capacity to adopt an array of structural complexities. Moreover, there has been a recent trend of increasing complexity of the very building blocks that construct the framework. It is the aim of the research presented in this dissertation to survey these two principle aspects of MOMs, diversity and complexity, by focusing upon the use of polycarboxylates and first row transition metals to synthesize several series of closely related materials imbued with varied levels of complexity. Through the use of single crystal X-ray diffraction and the charcterization of the materials\u27 properties, the structure-function relationship has been probed. Finally, novel design strategies incorporating supermolecular building blocks for the creation of a new generation of MOMs has been addressed