Electronic Thesis and Dissertation Repository

Degree

Master of Science

Program

Chemistry

Supervisor

Stillman, Martin

Abstract

Cyclic tetrapyrroles, like porphyrins, phthalocyanines, and chlorins, are of great interest for dye-sensitized solar cell (DSSC) applications due to their highly versatile structure, tunable π based spectroscopic and electrochemical properties, and excellent stabilities. As well, they have a structural analogy with chlorophyll, a natural photosensitizer. Chlorophylls exhibit a red and intense lowest energy absorption band that is one of the ideal properties of a dye for application in DSSCs. However, because chlorophylls are unstable, it is necessary to design similar but more stable tetrapyrroles with these ideal properties. The relationship between chlorophyll’s geometric structure and spectral properties were first explored using density functional theory (DFT) calculations. Understanding the unique electronic structure of the chlorophylls will help guide future designs of synthetic tetrapyrroles. The electronic structure of synthetic and fictive porphyrins and chlorins with β-substitutions were then probed using magnetic circular dichroism and DFT calculations.

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