Date of Award

1997

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

First Advisor

Wang, Suning,

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

We have been interested in the development of soluble precursors for the production of YBa$\sb2$Cu$\sb3$O$\sb{7-\delta}$ and Bi$\sb2$(Ca,Sr)$\sb{\rm n+1}$Cu$\sb{\rm n}$O$\sb{\rm (2n + 4) + \delta}$, superconductor materials. Several heterometallic and homometallic complexes containing the constituent metals of these superconductors and bifunctional ligands such as aminoalcohols, acetates and thioethers have been isolated and structurally characterized. The thermal decomposition properties and magnetic properties of some of these compounds have been investigated. The first ligand system investigated involved 1,3-bis(dimethylamino)-2-propanol (bdmapH). By varying the ratio of bdmapH, Cu(OCH$\sb3)\sb2$, and M(O$\sb2$CCF$\sb3)\sb2$ (M = Ca, Sr) several heterometallic complexes have been obtained, including Sr$\sb2$Cu$\sb2$(bdmap)$\sb4$(O$\sb2$CCF$\sb3)\sb4$, CaCu(bdmap)$\sb2$(O$\sb2$CCF$\sb3)\sb3$(H$\sb2$O), Sr$\sb2$Cu$\sb4$(bdmap)$\sb6$-(O$\sb2$CCF$\sb3)\sb4(\mu\sb 3$-OH)$\sb2$(THF)$\sb2$ and SrCu$\sb2$(bdmap)$\sb3$(O$\sb2$CCF$\sb3)\sb3$(THF). With the exception of Sr$\sb2$Cu$\sb4$(bdmap)$\sb6$(O$\sb2$CCF$\sb3)\sb4$($\mu\sb 3$-OH)$\sb2$(THF)$\sb2$, these compounds thermally decompose to form mixtures of fluorides and oxides. An analogous acetate compound SrCu$\sb2$(bdmap)$\sb3$(O$\sb2$CCH$\sb3)\sb3$(THF) has been produced, which forms the corresponding oxide at high temperature. A bismuth dimer, Bi$\sb2$(bdmap)$\sb2$(O$\sb2$CCH$\sb3)\sb4$(H$\sb2$O), has also been obtained. Superconducting powder of the Bi$\sb2$Sr$\sb2$CaCu$\sb2$O$\sb{8 + \delta}$ and epitaxial superconducting films of the YBa$\sb2$Cu$\sb3$O$\sb{7-\delta}$ superconductor have been produced using the bdmap and acetate ligands as cross-linking reagents. The second ligand system investigated involved di-2-pyridylmethanediol. Only homonuclear complexes have been obtained by using this ligand, including the mononuclear compound Cu ((2-py)$\sb2$CO(OH)) $\sb2$(HO$\sb2$CCH$ \sb3)\sb2\cdot$CH$\sb2$Cl$\sb2$, the tetranuclear compound Cu$\sb4$ ((2-py)$\sb2$CO(OH)) $\sb2$(O$\sb2$CCH$\sb 3)\sb6$(H$\sb2$O)$\sb2\cdot$CH$\sb2$Cl$\sb2$, and the bismuth dimer Bi$\sb2$ ((2-py)$\sb2$CO(OH)) $\sb2$(O$\sb 2$CCF$\sb3)\sb4\cdot$(THF)$\sb2.$ The tetranuclear Cu$\sb4$ compound was found to be dominated by ferromagnetic exchanges. The third ligand system examined involved 2,2$\sp\prime$-thiodiethanol (tdeH$\sb2$). Heterometallic complexes Pr$\sb2$Cu$\sb4$(tde)$\sb3$(tdeH)$\sb2$(hfacac)$\sb4(\mu\sb6 $-O) and Ba$\sb2$Cu$\sb2$(tdeH)$\sb4$(hfacac)$\sb4$ have been obtained using this ligand. The six metal centers in Pr$\sb2$Cu$\sb4$(tde)$\sb3$(tdeH)$\sb2$(hfacac)$\sb4(\mu\sb6$-O) are arranged in a octahedron and are linked by $\mu\sb6$-oxide and 2,2$\sp\prime$-thiodiethanolato ligands. A metallomacrocyclic Cu$\sb4$ compound, Cu$\sb4$(tde)$\sb2$(hfacac)$\sb4$ has been produced. Attempts have been made to produce bismuthine complexes with an amino or pyridyl functional group that can coordinate to copper. The reaction of 4-Li-C$\sb6$H$\sb4$CH$\sb2$N(2-PY)$\sb2$ with BiCl$\sb3$ produces the compound Bi$\sp{\rm III}$ (p-C$\sb6$H$\sb4$CH$\sb2$N(2-py)$\sb2\rbrack\sb3.$ The ability of this compound to coordinate CuCl$\sb2$ has been investigated. The complex Bi$\sp{\rm V}$ (p-C$\sb6$H$\sb4$CH$\sb2$N(2-py)$\sb2\rbrack\sb3$(O$\sb2$CCH$\sb3)\sb2$ has also been produced.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1997 .B725. Source: Dissertation Abstracts International, Volume: 59-08, Section: B, page: 4100. Adviser: Suning Wang. Thesis (Ph.D.)--University of Windsor (Canada), 1997.

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