| This dissertation describes the synthesis, characterization, and reactivity of a series of homobimetallic and mononuclear Rh(I) complexes that are assembled utilizing hemilabile ligands and the Weak-Link Approach to supramolecular coordination chemistry. The first two chapters of the thesis present synthetic and theoretical studies, focused on elucidating the fundamental aspects of the interactions between hemilabile ligands and transition metal centers. A series of new hemilabile ligands has been prepared that involve a systematic change in the steric and electronic properties of the central arene unit. These studies conclude that the organization of the reactants in the Weak-Link Approach is primarily metal driven, and the types and strengths of the metal-ligand interactions can be varied in a predictable way. Additionally, a theoretical study on four of these large bimetallic complexes was initiated to gain a detailed understanding of the energetics and bonding present in these systems that are difficult, if not impossible, to determine experimentally. The calculations yielded six optimized structures and a detailed picture of the ligand-ligand interactions in the condensed macrocycle. The resulting structures provide detailed information about the framework of van der Waals contacts in these constrained geometries.; In chapter 4, a study is presented that aims to determine quantitatively the energetics associated with the conversion of one of the dinuclear species to its thermodynamic mononuclear complex. This study uses a naphthalene-based hemilabile ligand to study the mechanism of conversion from slipped dimer to monomer. These experiments conclude that the conversion proceeds via an associative pathway that can be initiated by phosphine containing nucleophiles and is primarily influenced by the steric properties of the incoming nucleophile.; Finally, a fluorescent hemilabile ligand based on anthracene has been prepared and used to make fluorescent macrocycles. These macrocycles have reactive metal centers decorating their backbones that can be used to mediate host-guest chemistry. This reactivity has been exploited to develop a highly divergent synthetic strategy focused on the preparation of triple-layered fluorescent metallocyclophanes. These structures have been used to study the communication between chromophores and metal centers in this unique geometry. |
