Isolated Neutral Organic Radical Unveiled Solvent-Radical Interaction in Highly Reducing Photocatalysis
Dr. Aslam C. Shaikh
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab, 140001 India
These authors contributed equally to this work.
Search for more papers by this authorDr. Md Mubarak Hossain
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
These authors contributed equally to this work.
Search for more papers by this authorDr. Jules Moutet
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorDr. Anshu Kumar
Department of Physics, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorBenjamin Thompson
Department of Optical Sciences, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorDr. Vanessa M. Huxter
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Department of Physics, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorCorresponding Author
Dr. Thomas L. Gianetti
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorDr. Aslam C. Shaikh
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab, 140001 India
These authors contributed equally to this work.
Search for more papers by this authorDr. Md Mubarak Hossain
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
These authors contributed equally to this work.
Search for more papers by this authorDr. Jules Moutet
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorDr. Anshu Kumar
Department of Physics, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorBenjamin Thompson
Department of Optical Sciences, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorDr. Vanessa M. Huxter
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Department of Physics, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorCorresponding Author
Dr. Thomas L. Gianetti
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85721 United States
Search for more papers by this authorAbstract
Diffusion-limited kinetics is a key mechanistic debate when consecutive photoelectron transfer (conPET) is discussed in photoredox catalysis. In situ generated organic photoactive radicals can access catalytic systems as reducing as alkaline metals that can activate remarkably stable bonds. However, in many cases, the extremely short-lived transient nature of these doublet state open-shell species has led to debatable mechanistic studies, hindering adoption and development. Herein, we document the use of an isolated and stable neutral organic nPrDMQA radical as a highly photoreducing species. The isolated radical offers a unique platform to investigate the mechanism behind the photocatalytic activity of organic photocatalyst radicals. The involvement of reduced solvent is observed, formed by single electron transfer (SET) between the short-lived excited state nPrDMQA radical and the solvent. In our detailed mechanistic studies, spectroscopic and chemical affirmation of solvent reduction is strongly evident. Reduction of aryl halides, including difluoroarenes is presented as a model study of the conPET method. Further, the activation of N2O, a greenhouse gas that is yet to be activated by photoredox catalysis, is showcased in the absence of a transition metal.
Conflict of Interests
The authors declare no conflict of interest.
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