Zurauskas, Jonas and Bohacova, Sona and Wu, Shangze and Butera, Valeria and Schmid, Simon and Domanski, Michal and Slanina, Tomas and Barham, Joshua P. (2023) Electron-Poor Acridones and Acridiniums as Super Photooxidants in Molecular Photoelectrochemistry by Unusual Mechanisms. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 62 (44). ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
Electron-deficient acridones and in situ generated acridinium salts are reported as potent, closed-shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open-shell, radical cationic, 'beyond diffusion' photocatalysis to closed-shell, neutral, diffusion-controlled photocatalysis. Bronsted acid activation of acridones dramatically increases excited state oxidation power (by +0.8 V). Upon reduction of protonated acridones, they transform to electron-deficient acridinium salts as even more potent photooxidants (*E1/2=+2.56-3.05 V vs SCE). These oxidize even electron-deficient arenes where conventional acridinium salt photooxidants have thusfar been limited to electron-rich arenes. Surprisingly, upon photoexcitation these electron-deficient acridinium salts appear to undergo two electron reductive quenching to form acridinide anions, spectroscopically-detected as their protonated forms. This new behaviour is partly enabled by a catalyst preassembly with the arene, and contrasts to conventional SET reductive quenching of acridinium salts. Critically, this study illustrates how redox active chromophoric molecules initially considered photocatalysts can transform during the reaction to catalytically active species with completely different redox and spectroscopic properties. Under photoelectrochemical conditions, dicyanated acridones are precatalysts for acridinium ions as closed-shell, highly potent arene photooxidants. Despite the lifetime permitting diffusion-controlled quenching, a preassembly with substrate nonetheless operates. Highlighting the profound influence of preassembly on photocatalysis, quenching diverts from single to double electron transfer reduction of the excited state to an acridinide anion.+image
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ARYL HALIDES; PHOTOREDOX; REDUCTION; DERIVATIVES; GENERATION; FLUORESCENCE; EFFICIENT; RADICALS; FAMILY; ANIONS; Acridinium; Acridone; Photoelectrochemistry; Photoredox Catalysis; Preassembly |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Mar 2024 15:09 |
| Last Modified: | 12 Mar 2024 15:09 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59839 |
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