Doctor of Philosophy (PhD)
This dissertation focuses on synthesis of multifunctional â-diketone and â-ketoenamine ligands and their reaction with metal ions, mainly Cu2+. Several new bi-, tri-, and tetrafunctional organosilicon â-diketone building blocks with â-diketone groups at approx. 109° (tetrahedral) were successfully synthesized. New thiophene based bifunctional ligands where the â-diketones are at about 145° are also reported here. We also prepared a range of new aryl-â-ketoenamines from their analogous â-diketones in very high yield using a simple microwave-assisted procedure. Reactions of organosilicon tris(â-diketone)s LH3 with Cu2+ were explored quite intensively. These ligands form metal-organic-polyhedra (MOPs) that are soluble in organic solvents, and insoluble metal-organic polymers, upon reaction with Cu2+. The possibility of self-correction of the structure of Cu â-diketones was also studied. It was found that microwave irradiation of the insoluble material (likely polymeric [Cu3L2]n) in dichloromethane generates a green soluble species (15%). AFM images of the newly generated materials reveal molecules that are ca. 5 nm in size, which matches the expected size of a metal-organic dodecahedron Cu30L20 as estimated by molecular modeling. This indicates that â-diketone-based metal-organic materials can undergo self-correction of their structure under microwave-assisted heating.
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Marcos, Yoseph Solomon, "Beta-Diketone and -Ketoenamine-Based Organic Building Blocks for Porous Metal Organic-Materials" (2009). LSU Doctoral Dissertations. 2660.