Title

Supramolecular complexes containing pyridine N-oxides.

Date of Award

2004

Degree Type

Thesis

Degree Name

M.Sc.

Department

Chemistry and Biochemistry

First Advisor

Loeb, S. J.,

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

In the first section, the coordination chemistry of a new, divergent, N,O ligand was investigated. Several metal complexes of 4,4 '-bipyridine N-monoxide, 2a, were characterised by X-ray crystallography, including CuI, Cu II, PdII, CdII, HgII, and EuIII. The observed non-covalent interactions and coordinative preferences of 2a were contrasted with those of 4,4' -bipyridine and 4,4'-bipyridine N,N '-dioxide. Each of the compounds has a unique molecular topology that can be applied to the generation of ordered, pre-designed solids. Examples of this methodology are given with respect to the CuI, Cu II, and HgII metal complexes. Chapter three is concerned with the design and synthesis of multi-dimensional, polyrotaxane architectures. A new [2]pseudorotaxane, 3b ⊂ DB24C8, was used as a divergent ligand to connect metal nodes into extended coordination frameworks. Three distinct polyrotaxane networks were synthesised, one two-dimensional net containing CdII in which one-dimensional polyrotaxane strands are pillared in the second dimension by 3b. Two different three-dimensional topologies were generated using five different lanthanide cations. Structures containing SmIII, Eu III, GdIII, TbIII are isomorphous and adopt an alpha-polonium type lattice. The slightly smaller lanthanide, Yb III, generates the previously unreported 3 4,6 6 three-dimensional net. The final chapter describes the integration of an electrostatic component into the formation of [2]pseudorotaxanes. A derivative of DB24C8, 4d , was synthesised in which there are pendant-SO3 - groups on each benzo ring. The association constants of several threads were measured with 4d. It was shown that through the introduction of an electrostatic contribution to the recognition process that [2]pseudorotaxanes could be formed in a competitive solvent such as acetic acid. The X-ray crystal structure of 3b ⊂ 4d is presented and confirms the interpenetrated nature of the [2]pseudorotaxane.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2004 .H64. Source: Masters Abstracts International, Volume: 43-03, page: 0851. Adviser: S. J. Loeb. Thesis (M.Sc.)--University of Windsor (Canada), 2004.