Graduate Program

Chemistry

Degree Name

Master of Science (MS)

Semester of Degree Completion

2013

Thesis Director

Kraig A. Wheeler

Thesis Committee Member

Mary E. Konkle

Thesis Committee Member

Radu F. Semeniuc

Thesis Committee Member

Zhiqing Yan

Abstract

The pursuit of chemical specificity and efficiency of chemical reaction in molecular crystals has attracted considerable attention over the last decade. The successful control of molecular alignment prior to such transformations continues to provide opportunities for near quantitative yields of new materials. This thesis reports the predictable self-assembly of aryl sulfonamide materials constructed from cinnamic acid and phenylpentadienoic acid fragments capable of forming supramolecular dimers that undergo unique photocyclization reactions. Use of racemic and enantiopure single-component building-blocks provides access to enantiocontrolled [2+2] photodimerized products.

Solid-state reaction precursors were prepared using conventional solution-based synthetic organic techniques. Component chirality (racemic or homochiral) was introduced by treatment of arylsulfonyl chloride intermediates with the appropriate alanine or valine (D or DL) to give photoactive 'fish-hook' shape molecules. Use of serine and secondary reactants emphasized the impact of additional hydrogen bond groups and co-crystalline systems to favorable alignment of reactants in the solid-state. Assessment by crystallographic and spectroscopic (one- and two-dimensional NMR) methods provided insight to the structural tendencies and photochemical behavior of the programmed molecular components.

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