Date of Award

5-2012

Degree Type

Dissertation

Embargo Date

8-17-2012

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Advisor(s)

Jon A. Zubieta

Second Advisor

Lawrence L. Tavlarides

Subject Categories

Chemistry | Organic Chemistry

Abstract

This work encompasses detailed investigations of the synthesis and structures of polyoxomolybdate materials. The design and synthesis of hybrid organic-inorganic materials constructed from various anionic polyoxomolybdate units and cationic secondary metal-ligand units, and the synthesis and ligand-exchange capacity of the giant polyoxomolybdate cluster Mo-132 are described. These studies aim to increase our understanding of the formation and physiochemical properties of these materials, and thereby aid in the ability to control and predict their structural chemistry.

The analysis of a number of structural determinants in the oxomolybdenum-organodiphosphonate system aims to expand the current knowledge of this family of materials. We have focused on variables such as: the organic tether length of alkyldiphosphonate ligands; the size, flexibility, and number of nitrogen donor groups of secondary organoimine ligands; the oxidation state of the cationic transition metal center; and the incorporation of fluoride into the molybdodiphosphonate substructure.

In order to explore the range of possible anionic charges that the polyoxomolybdate Mo-132 cluster may posses, ligand-exchange reactions were conducted. This has been accomplished through the incorporation of various ratios of ligands contributing different degrees of anionic charge into the molybdate framework. Assorted structural characterization techniques reveal a range of ligand exchange based on the pH of the reaction solution.

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Open Access

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