Date of Completion

12-27-2012

Embargo Period

12-27-2012

Keywords

porphyrins, chlorins, bacteriochlorins, heterocycles

Major Advisor

Christian Brueckner

Associate Advisor

Amy Howell

Associate Advisor

Mark W. Peczuh

Field of Study

Chemistry

Degree

Doctor of Philosophy

Open Access

Open Access

Abstract

Since the serendipitous discovery of oxazole-containing porphyrins over 30 years ago, this class of porphyrinoid macrocycles remained largely unexplored. This thesis is the first systematic study of the syntheses and optical properties of this class of macro­cycles. Specifically, this thesis investigates the scope and limits of synthesizing various oxazole containing chlorin and bacteriochlorin chromophores. The multi-step syntheses described are based on the OsO4-mediate dihydroxylation of meso-tetraphenylporphyrin to form diolchlorin . This diol is converted into various oxazolones and/or a-substituted oxazolines via one of two principal pathways; through MnO4— mediated oxidation or NaIO4-mediated oxidative cleavage. Similar reaction sequence also takes place on the opposing pyrrole unit for the formation of bis-oxazolochlorins and -bacteriochlorins. These oxazole(s)-containing macrocycles are optically tunable in 20-30 nm increments in the range of 650-810 nm.

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