Extent of carbon nitride photocharging controls energetics of hydrogen transfer in photochemical cascade processes.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
24 Nov 2023
24 Nov 2023
Historique:
received:
12
04
2023
accepted:
07
11
2023
medline:
25
11
2023
pubmed:
25
11
2023
entrez:
24
11
2023
Statut:
epublish
Résumé
Graphitic carbon nitride is widely studied in organic photoredox catalysis. Reductive quenching of carbon nitride excited state is postulated in many photocatalytic transformations. However, the reactivity of this species in the turn over step is less explored. In this work, we investigate electron and proton transfer from carbon nitride that is photocharged to a various extent, while the negative charge is compensated either by protons or ammonium cations. Strong stabilization of electrons by ammonium cations makes proton-coupled electron transfer uphill, and affords air-stable persistent carbon nitride radicals. In carbon nitrides, which are photocharged to a smaller extent, protons do not stabilize electrons, which results in spontaneous charge transfer to oxidants. Facile proton-coupled electron transfer is a key step in the photocatalytic oxidative-reductive cascade - tetramerization of benzylic amines. The feasibility of proton-coupled electron transfer is modulated by adjusting the extent of carbon nitride photocharging, type of counterion and temperature.
Identifiants
pubmed: 38001091
doi: 10.1038/s41467-023-43328-6
pii: 10.1038/s41467-023-43328-6
pmc: PMC10674013
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
7684Informations de copyright
© 2023. The Author(s).
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