Graduation Year

2008

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemistry

Major Professor

Michael J. Zaworotko, Ph.D.

Committee Member

Srikanth Hariharan, Ph.D.

Committee Member

Mohamed Eddaoudi, Ph.D.

Committee Member

Julie P. Harmon, Ph.D.

Committee Member

K. Travis Holman, Ph.D.

Keywords

Crystal structure, Coordination polymer, Crystal engineering, Supramolecular isomerism, Topology

Abstract

The interest in metal-organic materials namely, coordination polymers and metal-organic frameworks has risen dramatically over the past few years. To a certain extent this interest is a consequence of the realization chemists have discovered how to play a form of molecular Lego® in which metal cations or metal clusters represent the bricks (or nodes) and organic ligands such as 4,4-bipyridine (bipy) or benzene-dicarboxylate represents the glue (or spacers). The "node-and-spacer" approach to self-assembly can be invoked in such a manner that a plethora of infinite architectures and discrete polyhedra can be generated from geometric principles, some of which are unprecedented in either natural or synthetic materials. The research presented within this dissertation primarily involves the use of coordination chemistry and supramolecular chemistry in the context of synthesizing metal-organic materials and deals with how subtle variations in reactants and procedures can have dramatic effects upon the materials formed. The effect of aromatic guest molecules on the crystal packing of 1D and 2D "metal-4,4`-bipyridine" coordination polymers has been addressed in terms of structural analysis and fluorescence spectroscopy. The phenomena of supramolecular isomerism resulting from the use of metal-carboxylate clusters as building blocks for a variety of metal-organic materials will be discussed. Finally, an analysis of the Host:Guest and suprasupermolecular properties of discrete nanostructures will be provided.

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