Date of Award
Doctor of Philosophy (PhD)
Jon A. Zubieta
Hydrothermal Synthesis, Metal-organic Frameworks, Transition Metals, X-Ray Crystallography
This work encompasses detailed investigations of the synthesis and structures of transition metal complexes which contain xylyldiphosphonate or organoarsonate ligands. The xylyldiphosphonate families of materials which were examined were the metal(II) series of Cu, Ni, Co, Mn, Cd and Zn, with an addition of an organo-nitrogen chelate. With success in these families of materials, a secondary metal of vanadium or molybdenum was added to these metal(II) systems to increase the complexity of the structure produced. For the organoarsonate series of compounds, the chemistry of the Mo/metal(II)/organoarsonate/organo-nitrogen chelate family of materials was expanded upon and preliminary studies were conducted into the V/metal(II)/organoarsonate/organo-nitrogen chelate group of materials.
The analysis of a number of structural determinants in the xylyldiphosphonate family of compounds aims to expand upon the current knowledge of metal-diphosphonate chemistry. We have focused on variables such as the xylyldiphosphonate ligand used- whether 1,4-, 1,3- or 1,2-xylyldiphosphonate. Furthermore, we have varied the denticity and size of the organo-nitrogen co-ligand. We have also investigated the incorporation of fluoride into the vanadium and molybdenum series of compounds. Through our examination of these systems we have discovered that all possible dimensionalities are represented in the xylyldiphosphonate series of compounds; we postulate that the unique flexibility of the xylyldiphosphonate ligands allows a number of unique structures to be produced.
In expanding upon the organoarsonate family of materials we have discovered the preferences for molecular structures in the Mo/metal(II)/organoarsonate/organo-nitrogen chelate family of materials. In our preliminary studies of the vanadium group of materials, a one-dimensional chain was produced and with a minor change in reaction conditions we saw a drastic structural change which yielded a mixed-dimensional structure consisting of clusters and chains. We conclude that minor changes in reaction conditions can lead to large structural changes with the use of hydrothermal synthesis.
Smith, Tiffany Marie, "Design and Synthesis of Solid State Materials Constructed from Transition Metals and Diphosphonate or Organoarsonate Ligands" (2013). Dissertations - ALL. 6.