Wu, Shangze and Zurauskas, Jonas and Domanski, Michal and Hitzfeld, Patrick S. and Butera, Valeria and Scott, Daniel J. and Rehbein, Julia and Kumar, Ajeet and Thyrhaug, Erling and Hauer, Juergen and Barham, Joshua P. (2021) Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants. ORGANIC CHEMISTRY FRONTIERS, 8 (6). pp. 1132-1142. ISSN 2052-4129
Full text not available from this repository. (Request a copy)Abstract
As a combination of visible light photoredox catalysis and synthetic organic electrochemistry, electrochemically-mediated photoredox catalysis emerged as a powerful synthetic technique in recent years, overcoming fundamental limitations of electrochemistry and photoredox catalysis in the single electron transfer activation of small organic molecules. Herein we report a tunable class of electroactivated photoredox catalyst, tri(para-substituted)biarylamines, that become superoxidants in their photoexcited states even able to oxidize molecules beyond the solvent window limits of cyclic voltammetry (such as polyfluorobenzene and trifluorotoluene). Furthermore, we demonstrate that precomplexation not only permits the excited state photochemistry of tris(para-substituted)biarylaminium cations to overcome picosecond lifetime, but enables and rationalizes the surprising photochemistry of their higher-order doublet (D-n) excited states, unlocking extremely high oxidative potentials (up to a record-breaking similar to+4.4 V vs. SCE).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOTOINDUCED ELECTRON-TRANSFER; C-H AMINATION; ORGANIC ELECTROSYNTHESIS; LIGHT; OXIDATION; DYNAMICS; ELECTROCHEMISTRY; PHOTOCHEMISTRY; REDUCTION; ACRIDINE |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 Aug 2022 09:29 |
| Last Modified: | 17 Aug 2022 09:29 |
| URI: | https://pred.uni-regensburg.de/id/eprint/46528 |
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