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Design and application of strongly reducing photoredox catalysts for small molecule and macromolecular synthesis


The synthesis and application of new families of strongly reducing organic photoredox catalysts are described in this dissertation. These compounds provide a platform on which catalytically relevant properties including redox potentials and absorption profiles can be tuned, as well as predicted in silico. The critical photophysical and electrochemical characteristics have been established for both dihydrophenazine and phenoxazine catalysts which enable their ability to be used as green alternatives to commonly used transition metal photocatalysts. Specifically, phenoxazines have been utilized to mediate organocatalyzed atom transfer radical polymerization (O-ATRP) for the production of well-defined polymers using visible light. To this end, a catalyst system able to synthesize acrylic polymers with predictable molecular weights and dispersities less than 1.10 has been developed. In addition, dihydrophenazines were shown to mediate trifluoromethylation and atom transfer radical addition reactions, while phenoxazines were able to mediate C-N and C-S cross coupling reactions in the presence of a nickel co-catalyst.


2019 Summer.
Includes bibliographical references.

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