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- Title
Picosecond reactions of excited radical ion super-reductants.
- Authors
Pfund, Björn; Gejsnæs-Schaad, Deyanira; Lazarevski, Bruno; Wenger, Oliver S.
- Abstract
Classical photochemistry requires nanosecond excited-state lifetimes for diffusion-controlled reactions. Excited radicals with picosecond lifetimes have been implied by numerous photoredox studies, and controversy has arisen as to whether they can actually be catalytically active. We provide direct evidence for the elusive pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. A strategy based on two distinct light absorbers, mimicking the natural photosystems I and II, is used to generate excited radicals, unleashing extreme reduction power and activating C(sp2)―Cl and C(sp2)―F bonds. Our findings provide a long-sought mechanistic understanding for many previous synthetically-oriented works and permit more rational future photoredox reaction development. The newly developed excitation strategy pushes the current limits of reactions based on multi-photon excitation and very short-lived but highly redox active species. Classical photochemistry requires nanosecond excited-state lifetimes for diffusion-controlled reactions. Here the authors provide direct evidence for the elusive pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit.
- Subjects
RADICAL ions; PHOTOINDUCED electron transfer; RADICALS (Chemistry); LEGAL evidence; PHOTOCHEMISTRY; MOLECULES
- Publication
Nature Communications, 2024, Vol 15, Issue 1, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-024-49006-5