N,N-Diaryl Dihydrophenazine photoredox catalysis for organocatalyzed atom transfer radical polymerization
Date
2019
Authors
Ryan, Matthew David, author
Miyake, Garret, advisor
Chen, Eugene, committee member
Kota, Arun, committee member
Snow, Christopher, committee member
Journal Title
Journal ISSN
Volume Title
Abstract
The synthesis, application, and mechanistic investigation of the 5,10-diaryldihydrophenazine catalyst family as applied to organocatalyzed atom transfer radical polymerization is presented in this dissertation. The N,N-Diaryl Dihydrophenazine catalyst family, which will be referred to in this dissertation as the phenazines, are an appealing class of molecules due to their strongly reducing excited states, accessed through modular syntheses enabling a wide range of photophysical and electrochemical properties. This class of molecules represented the first example of organic catalysts capable of operating a controlled, visible light driven, organocatalyzed atom transfer radical polymerization for the precision syntheses of (meth)acrylic polymers. Phenazine catalysts were shown to polymerize (meth)acrylic monomers to polymers of very low dispersities (< 1.10) in a process with quantitative initiator efficiency; both features crucial to produce precision polymeric materials poised for myriad applications. Supported by computational efforts, mechanistic understanding and structure-property-catalyst activity relationships were identified and harnessed to design optimal polymerization conditions, which have laid the groundwork for new research efforts into highly reducing, visible light absorbing, organic photocatalysts.
Description
Rights Access
Subject
catalysis
ATRP
photoredox