Title

Chiral Porphyrins with Chiral Caps: Synthesis and Chiral Recognition Studies

Document Type

Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

Date of Award

Spring 2015

Abstract

This project centers on the synthesis of chiral porphyrins characterized by the spatial positioning of asymmetric centers above the porphyrin surface which effectively serves to cap the porphyrin. Thus, these hosts have asymmetric centers positioned directly above the metal center of the porphyrin. The introverted nature of these hosts asymmetrically positions recognition elements within the interior of the host cavity from above the porphyrin where they can work in tune with the metal center for cooperative guest binding. A novel aspect of the hosts is their fairly rigid nature such that recognition elements are in well-defined positions. Furthermore the hosts are modular in design. For the creation of the hosts, a common porphyrin isocyanate was reacted with a variety of commercially available chiral amines and chiral amino acids; the hosts are thus available in diversity in high yield with minimal synthetic effort. This work involved the synthesis of these hosts and the study of their chiral guest recognition properties. Chiral recognition properties were examined using UV/Vis and NMR spectroscopic studies. In addition to studying the recognition of Zn-TPP, Cadmium-TPP was synthesized and studied with different urea guests in order determine the coordinating ability of carbonyl and sulfonyl groups for metallo-porphyrin centers which will aid future porphyrin host design. This study was aimed at helping to better understand how the λmax of porphyrin hosts correlates to metallo-center coordination.

Advisor

Stephen D. Starnes

Subject Categories

Chemistry | Physical Sciences and Mathematics

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