Date of Award

Summer 8-15-2013

Author's School

Graduate School of Arts and Sciences

Author's Department

Chemistry

Degree Name

Doctor of Philosophy (PhD)

Degree Type

Dissertation

Abstract

Photosynthetic chromophore analogs are studied, starting with simplified structures and systematically building complexity to elucidate overarching design principles. The general goals are to achieve an artificial light-harvesting system that exhibits broad spectral coverage, including extension well into the photon rich red and near-infrared portions of the solar spectrum. For example, the spectral properties of chlorophylls are primarily a consequence of the 131-oxophorbine base macrocycle, with further tuning provided by the dramatic difference in auxochromic effects of a given substituent at the 7- versus 3-position, consistent with Gouterman's four-orbital model.

While light-harvesting antennas in photosynthetic bacteria generally have near-quantitative transfer of excitation energy among pigments, only a fraction of the solar spectrum is typically absorbed. The new biohybrid antennas retain the energy-transfer and self-assembly characteristics of the native antenna complexes, offer enhanced coverage of the solar spectrum, and illustrate a versatile paradigm for the construction of artificial light-harvesting systems. Such complexes can ultimately connect with complimentary efforts in the realms of energy conversion and storage towards a successful utilization of natural and bio-inspired photosynthesis for energy production.

Language

English (en)

Chair and Committee

Dewey Holten

Committee Members

Ronald Lovett, Lee Sobotka, Liviu Mirica, Jay Turner, Pratim Biswas

Comments

Permanent URL: https://doi.org/10.7936/K76D5RF2

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