UCLA

Polyhedral boron clusters are a unique class of three-dimensional aromatic molecules which have profound tunability of their chemical and material properties through the selective functionalization of the boron vertices. In this dissertation, the syntheses and characterization of several boron cluster derivatives based on the parent dodecaborate anion ([B12H12]2-] are discussed. Chapters 1 and 2 focus on boron cluster derivatives synthesized by full functionalization of all twelve B-H vertices on the cluster, while Chapter 3 discusses the effects of select functionalization of specific boron vertices. More specifically, Chapter 1 focuses on the structural elucidation and material properties of a 2D-coordination polymer composed of Zn(II) and a perhydroxylated boron cluster ([B12(OH)12]2-), which represents the first transition metal-coordinated species within this family of boron clusters. Chapter 2 discusses a new molecule within the class of aryl/alkyloxy-functionalized dodecaborate derivates, B12(OCH3)12. The synthesis of this boron cluster was optimized and its electrochemical properties were thoroughly characterized by cyclic voltammetry. Importantly, [B12(OCH3)12]0 was observed to undergo electrochemical cycling in the solid state, a previously unobserved phenomenon among boron clusters. It was successfully incorporated as the cathode-active material in an all-solid-state Li-ion cell, which showed good reversibility and Coulombic efficiency. Finally, Chapter 3 discusses a new class of neutral, di-functionalized dodecaborate isomers, B12H10(NMe3)2, which show structural similarities to the well-known icosahedral carboranes, yet possess enhanced reactivity and overall stability due to electronic directing group effects.