Graduation Year

2004

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemistry

Major Professor

Michael J. Zaworotko

Keywords

Supramolecular chemistry, Crystal engineering, Calixarene, Metal-organic network, Porosity

Abstract

The rational design of functional solids based upon the development of strategies for controlling intermolecular interactions and structural arrangement of simple molecular building units, represents a salient feature in the context of supramolecular chemistry and crystal engineering. Consideration of chemical functionality, geometrical capability and knowledge of the interplay between two or more sets of supramolecular interactions specific of preselected chemical components will facilitate further extension of crystal engineering towards the construction of supramolecular materials possessing valuable properties. Calixarenes represent excellent building blocks for the design of solid-state architectures, in particular calix-4-arenes crystallize easily and the introduction of a wide range of director functions is relatively simple.

For example, amphiphilic and pseudo-amphiphilic calixarenes may be synthesized by selective functionalization at either face of the skeleton and a second functionality may then be introduced at the opposite face. Careful examination of the crystal packing of a series of calix-4-arene derivatives systematically modified with various alkyl chain lengths at the lower rim and selected functional groups at the upper rim will be considered in the broader perspective of crystal engineering strategies and development of novel materials. Metal-organic networks are typically based upon the cross-linking of transition metal-based nodes by "spacer" organic ligands. Since there is an inherent control over the chemical nature of the components of such metal-organic structures, it is possible to design infinite architectures that possess well-defined topologies and contain cavities suitable for incorporation of guest molecules.

Investigation of metal-organic networks based upon rigid ligands possessing two types of coordination sites (nicotinate and dinicotinate) and conformationally labile ligands possessing saturated fragments (glutarate and adipate) will be addressed in the context of topological approaches to the design of multi-dimensional networks with particular emphasis upon their resulting properties.

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