Document Type

Dissertation

Date of Degree

Summer 2014

Degree Name

PhD (Doctor of Philosophy)

Degree In

Chemistry

First Advisor

Leonard R. MacGillivray

Abstract

Solid-state chemistry presents itself as a rapidly growing field of materials chemistry. When compared to solution phase chemistry, solid-state chemistry offers the potential for significant benefits to the researcher including better stereoselectivity and product selectivity as well as the ability to synthesize products that may be difficult to obtain in the solution phase. The solid-state [2+2] photocycloaddition reaction, as first demonstrated by Schmidt, exemplifies these benefits through the selective photoreaction of olefins. Within these benefits however, certain limitations such as unpredictable crystal packing and limited functional group diversity remain, limiting the applications and expansion of solid-state chemistry.

It has been our goal to overcome these limitations through the use of the template method, crystal engineering, and post-synthetic modification (PSM) techniques. As first developed by MacGillivray, the template method relies on supramolecular interactions within cocrystals to guide photostable olefins into photoacitve assemblies. While it does not provide overall control of crystal packing, it guides local packing within the crystal. Our work has focused on utilizing both the template method, as well as PSM techniques to develop a library of analogous, yet functionally diverse molecules to undergo the [2+2] photocycloaddition reaction in the solid state. To this end, we have performed the click reaction to generate a library of molecules and incorporate the 1,4 disubstituted 1,2,3 triazole ring within our olefinic systems. Our efforts to study the triazole ring as a functional group in the solid state and also to perform the [2+2] photocycloaddition on a click-derived molecule will be described within this thesis.

Additionally, we have sought to expand the template method through the development of the first non-covalently templated intramolecular [2+2] photocycloaddition reaction in the solid state. Our work towards understanding the effects on crystal packing due to functional group diversity on a template, as well as the design of a novel molecule able to undergo an intramolecular [2+2] photocycloaddition reaction will be presented in this thesis.

Keywords

Crystallography, Supramolecular

Pages

xv, 147 pages

Bibliography

Includes bibliographical references (pages 128-135).

Copyright

Copyright 2014 Rebecca Christine Laird

Included in

Chemistry Commons

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