Identifier

etd-07102009-111915

Degree

Doctor of Philosophy (PhD)

Department

Chemistry

Document Type

Dissertation

Abstract

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.

Date

2009

Document Availability at the Time of Submission

Secure the entire work for patent and/or proprietary purposes for a period of one year. Student has submitted appropriate documentation which states: During this period the copyright owner also agrees not to exercise her/his ownership rights, including public use in works, without prior authorization from LSU. At the end of the one year period, either we or LSU may request an automatic extension for one additional year. At the end of the one year secure period (or its extension, if such is requested), the work will be released for access worldwide.

Committee Chair

Maverick, Andrew

Included in

Chemistry Commons

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