Three Assembly Modes of Hydrothermally Synthesized Inorganic Organic Hybrid Materials: Direct Metal-Ligand Coordination, Supramolecular Chemistry, and in situ Ligand Synthesis

This dissertation is based on the hydrothermal synthesis and subsequent characterization of a range of f-block (and to a lesser extent, d-block) inorganic-organic coordination polymers. These coordination polymers or 'hybrid materials' consist of extended architectures containing organic ligand and metal centers. As various pathways towards extended structure assembly are applied, we hope to produce a wide range of architectural motifs. In turn, the array of topologies may provide more insight towards our proposed synthetic methods, but also enrich our knowledge of fundamental solid state uranium chemistry. As follows, the syntheses, topographic features, and luminescence properties of the resulting compounds are discussed herein.;The realm of uranyl-bearing hybrid materials is dominated by the presence of uranyl carboxylates. The affinity for --COOH functional groups for the uranyl cation, UO22+ explains the ubiquitous utilization of this particular group in uranyl coordination polymers. We embrace this same approach of direct ligand-metal coordination and synthesize new uranyl carboxylates. Moreover, we build upon the foundation of carboxylate organic ligands and observe the influence of steric crowding and the presence of additional UO22+ coordination sites on overall structural topology.;Beyond a structural exploration, we also examine the formation of uranyl-carboxylates. A series of three uranyl-carboxylates, including one with a UO2 2+-UO22+ cation-cation interaction (CCI), affords us the opportunity to apply hydrothermal in situ Raman spectroscopy. By monitoring product formation with this technique, we may gain more insight into formation mechanisms and stability considerations of hybrid materials. This is especially interesting with respect to UO 22+-UO22+ CCIs as formation mechanisms for this type of uranyl oligomerization remain elusive.;On the other end we investigate the luminescence properties of both homo- and heterometallic uranyl-bearing compounds. UO22+ is a highly emissive entity which can be influenced by its local geometry. The addition of a secondary metal center, such as Sm3+, would afford the opportunity to examine the potential energy transfer between emissive sites. Furthermore, the incorporation of a trivalent lanthanide with a spherical coordination mode could produce structures of higher dimensionality, thus also contributing to the rich portfolio of uranyl coordination polymers.;With this rich diversity of uranyl-carboxylates we look to incorporate another mode of structural assembly: supramolecular interactions. As follows, -Cl and --NH2 groups would serve as so-called 'terminating' sites for UO22+, yet host supramolecular interactions within the resulting coordination polymer. Thus, this series of compounds incorporating intermolecular interactions could be compared to a related series of compounds featuring traditional metal-ligand coordination.;The last investigation represents a change of pace as it shifts the focus from direct assembly to in situ ligand synthesis (ISLS). We utilize Huisgen 1,3-dipolar cycloaddition to form a series of bimetallic uranyl-bearing coordination polymers. As a consequence of an abbreviated scheme, strictly homometallic transition hybrid materials were produced. These results, however, are encouraging within the context of material synthesis and will continue to be utilized in future investigations.