AbstractsChemistry

Tridecameric inorganic hydroxo/aquo nanoclusters comprise a very small fraction of compounds under the large and varied umbrella of inorganic clusters. The Anderson-Evans cluster is a subset of these larger polymetallic tridecameric clusters. A novel synthesis of M 13 nanoclusters containing the Anderson-Evans cluster as cores has been discovered. This synthesis proceeds with the aid of a key organic reagent, which reacts with the nitrate counter anions of the starting material removing them from the solution. This forces the formation of a higher nuclearity species. Research continues to focus on the generality of the reaction as it applies to both inorganic and organic synthesis, as well as on extensive characterization of the novel clusters by a variety of analytical methods. These nanoelusters have proven to be useful as single-source precursors for the preparation of thin film oxides due to their high purity and crystallinity. Chapter I is a literature review of Anderson-Evans clusters in the context of how they comprise the core substructure in the reported tridecameric nanoclusters. Attention is also given to the numerous clusters or complexes that are absent from this series. Chapter II chronicles the discovery and synthesis of [Ga 13 (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 ](NO 3 ) 15 a nanocluster previously thought to be unstable. Chapter III describes the modification of the reaction to prepare other tridecameric inorganic nanoclusters with increases in yield and purity. Chapter IV reports the isolation of a series of new heterometallic tridecameric nanoclusters and a potential predictive strategy for tuning the metal ratios in the crystalline products. Chapter IV also highlights the application of the nanoclusters as precursors to thin film oxides. Initial characterization of tridecameric inorganic nanoclusters using powder and single crystal XRD, NMR, ToF-SIMS, EPMA and SEM instrumentation is explained in Chapter V. Finally, Chapter VI is a summary and a report of the current standing of a different project aimed at developing a template-assisted self-assembly of organic nanocages using two different ligand classes that were explored. This dissertation includes previously published and co-authored material.