|
|||||
|
|
Solvent effects on the intramolecular charge transfer character of N,N-diaryl dihydrophenazine catalysts for organocatalyzed atom transfer radical polymerization |
|
| Authors: | Matthew D Ryan Jordan C Theriot Chern-Hooi Lim Haishen Yang Andrew G Lockwood Nathaniel G Garrison Sarah R Lincoln Charles B Musgrave Garret M Miyake |
| Institution: | 1. Department of Chemistry and Biochemistry, University of Colorado Boulder, Colorado, 80309;2. Department of Chemistry and Biochemistry, University of Colorado Boulder, Colorado, 80309
Department of Chemical and Biological Engineering, University of Colorado Boulder, Colorado, 80309 Materials Science and Engineering Program, University of Colorado Boulder, Colorado, 80309 |
| Abstract: | The nature of intramolecular charge transfer (CT) of N,N-diaryl dihydrophenazine photocatalysts (PCs) in different solvents is explored in context of their performance in organocatalyzed atom transfer radical polymerization (O-ATRP). PCs having a computationally predicted lowest energy excited state exhibiting CT character can operate a highly controlled O-ATRP in a wide range of solvent polarities, from non-polar hexanes to highly polar N,N-dimethylacetamide. For PCs having a computationally predicted lowest energy excited state not possessing CT character, their ability to operate a controlled O-ATRP is decreased. This study confirms the importance of CT character in the excited state for N,N-diaryl dihydrophenazine PCs, and a deeper understanding of the activity of CT PCs has enabled the synthesis of polymers of low dispersity (<1.10) in a controlled fashion. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3017–3027 |
| Keywords: | ATRP catalysis organocatalysis photopolymerization radicals |