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Characterization and Photodynamics of Reactive Intermediates for Various Carbonyl-Based Systems: Alkyl Azides, Vinyl Azides, and Beta-Ketoester Moieties

Gatlin, DeVonna M, M.S.
http://orcid.org/0000-0002-6700-0924
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1535380770508755

Abstract Details

2018, PhD, University of Cincinnati, Arts and Sciences: Chemistry.
The research projects presented in this dissertation looks at the photodynamics of various carbonyl-based compounds. The following research studies were designed to investigate the triplet reactivity and the reactive intermediates formed from carbonyl derived compounds. The carbonyl compounds of interest are tethered at the alpha position, to several targeted functional groups. The functional groups explored include alkyl azides, vinyl azides, and beta-ketoester moieties. These different groups were used to evaluate the impact that molecular architecture has on the photo-induced properties of carbonyl compounds. Below is a summary of the projects investigated, centering around two themes; characterization of triplet reactive intermediates and the elucidation of the photodynamics that control the triplet reactivity for carbonyl-based compounds: 1) Intra- vs. inter- molecular sensitization of N-heterocyclic product formation via UV and/or visible light. These systems exhibit product selectivity shifts in the formation of N-heterocyclic as a function of chemical modification and/or external visible light photocatalyst. 2) Ring strain effects on the photostability and reactivity of triplet vinylnitrenes under cryogenic temperatures. These systems exhibit the stable formation of triplet vinylnitrenes at low temperature, independent of ring size. Yet, the secondary photoreactivity is affected by ring strain, the more ring strain the more reactivity. 3) Photo-induced steady and excited state tautomerization of beta-ketoesters. These systems exhibit photodynamics that is affected by solvent, excitation wavelength, or local environment. The nature of H-bonding is the major factor that controls the kinetics and the reactive intermediates formed in these systems.
Anna Gudmundsdottir, Ph.D. (Committee Chair)
Hairong Guan, Ph.D. (Committee Member)
James Mack, Ph.D. (Committee Member)
412 p.
Organic Chemistry
Photochemistry; Photocatalysis; Azide; Physical Organic Chemistry; Visible Light LED; Time Resolved Spectroscopy

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Citations

  • Gatlin, D. M. (2018). Characterization and Photodynamics of Reactive Intermediates for Various Carbonyl-Based Systems: Alkyl Azides, Vinyl Azides, and Beta-Ketoester Moieties [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1535380770508755

    APA Style (7th edition)

  • Gatlin, DeVonna. Characterization and Photodynamics of Reactive Intermediates for Various Carbonyl-Based Systems: Alkyl Azides, Vinyl Azides, and Beta-Ketoester Moieties . 2018. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1535380770508755.

    MLA Style (8th edition)

  • Gatlin, DeVonna. "Characterization and Photodynamics of Reactive Intermediates for Various Carbonyl-Based Systems: Alkyl Azides, Vinyl Azides, and Beta-Ketoester Moieties ." Doctoral dissertation, University of Cincinnati, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1535380770508755

    Chicago Manual of Style (17th edition)

ucin1535380770508755
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This open access ETD is published by University of Cincinnati and OhioLINK.