Published September 2, 2022
| v2
Journal Article
Open
Mechanism of a Luminescent Dicopper System That Facilitates Electrophotochemical Coupling of Benzyl Chlorides via a Strongly Reducing Excited State
Chicago
Abstract
Photochemical radical generation has become a modern staple in chemical synthesis and methodology. Herein, we detail the photochemistry of a highly reducing, highly luminescent dicopper system [Cu₂] (Eₒₓ* ≈ −2.7 V vs SCE; τₒ ≈ 10 μs) within the context of a model reaction: single-electron reduction of benzyl chlorides. The dicopper system is mechanistically well defined. As we show, it is the [Cu₂]* excited state that serves as the outer-sphere photoreductant of benzyl chloride substrates; the ground-state oxidized byproduct, [Cu₂]⁺, is electrochemically recycled, demonstrating a catalytic electrophotochemical C–C coupling process.
Additional Information
The authors are grateful to the National Institutes of Health (NIGMS: R01-109194) for support of this research. M.D.Z. acknowledges the Resnick Sustainability Institute at Caltech and the National Science Foundation (DGE-1745301) for support via Graduate Fellowships. V.M.C. acknowledges the John Stauffer Charitable Trust and Caltech's Summer Undergraduate Research Fellowships program for summer research funding. The Beckman Institute Laser Resource Center and Jay R. Winkler are acknowledged for providing support with steady-state and time-resolved luminescence experiments. We acknowledge Dr. Joseph Derosa for insightful discussions.Files
nihms-1900343.pdf
Additional details
- Eprint ID
- 117444
- DOI
- 10.1021/acscatal.2c03215
- Resolver ID
- CaltechAUTHORS:20221017-10817000.2
- PMCID
- PMC10306173
- NIH
- R01-109194
- Resnick Sustainability Institute
- NSF Graduate Research Fellowship
- DGE-1745301
- John Stauffer Charitable Trust
- Caltech Summer Undergraduate Research Fellowship (SURF)
- Created
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2022-10-20Created from EPrint's datestamp field
- Updated
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2022-10-20Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute