The Rational Design of Reducing Organophotoredox Catalysts Unlocks Proton-Coupled Electron-Transfer and Atom Transfer Radical Polymerization Mechanisms.


Journal

Journal of the American Chemical Society
ISSN: 1520-5126
Titre abrégé: J Am Chem Soc
Pays: United States
ID NLM: 7503056

Informations de publication

Date de publication:
25 Jan 2023
Historique:
pubmed: 7 1 2023
medline: 7 1 2023
entrez: 6 1 2023
Statut: ppublish

Résumé

Photocatalysis has become a prominent tool in the arsenal of organic chemists to develop and (re)imagine transformations. However, only a handful of versatile organic photocatalysts (PCs) are available, hampering the discovery of new reactivities. Here, we report the design and complete physicochemical characterization of 9-aryl dihydroacridines (9ADA) and 12-aryl dihydrobenzoacridines (12ADBA) as strong reducing organic PCs. Punctual structural variations modulate their molecular orbital distributions and unlock locally or charge-transfer (CT) excited states. The PCs presenting a locally excited state showed better performances in photoredox defunctionalization processes (yields up to 92%), whereas the PCs featuring a CT excited state produced promising results in atom transfer radical polymerization under visible light (up to 1.21

Identifiants

pubmed: 36608266
doi: 10.1021/jacs.2c11364
pmc: PMC9881005
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

1835-1846

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Auteurs

Tommaso Bortolato (T)

Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.

Gianluca Simionato (G)

Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.

Marie Vayer (M)

Institut de Science et d'Ingénierie Supramoléculaires (ISIS), CNRS UMR 7006, Université de Strasbourg, 8 allée Gaspard Monge, 67000Strasbourg, France.

Cristian Rosso (C)

Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.

Lorenzo Paoloni (L)

Dipartimento di Fisica e Astronomia G. Galilei, University of Padova, Via Marzolo 8, 35131, Padova, Italy.

Edmondo M Benetti (EM)

Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.

Andrea Sartorel (A)

Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.

David Lebœuf (D)

Institut de Science et d'Ingénierie Supramoléculaires (ISIS), CNRS UMR 7006, Université de Strasbourg, 8 allée Gaspard Monge, 67000Strasbourg, France.

Luca Dell'Amico (L)

Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.

Classifications MeSH