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The Rational Design of Reducing Organophotoredox Catalysts Unlocks Proton-Coupled Electron-Transfer and Atom Transfer Radical Polymerization Mechanisms by Tommaso Bortolato; Gianluca Simionato; Marie Vayer; Cristian Rosso; Lorenzo Paoloni; Edmondo M. Benetti; Andrea Sartorel; David Lebœuf; Luca Dell’Amico is a Chemistry article available to read on EtoBox.

What is The Rational Design of Reducing Organophotoredox Catalysts Unlocks Proton-Coupled Electron-Transfer and Atom Transfer Radical Polymerization Mechanisms about?

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 Đ, and 98% I\*). Unlike all the PC classes reported so far, 9ADA and 12ADBA feature a free NH group that enables a catalytic multisite proton-coupled electron transfer (MS-PCET) mechanism. This manifold allows the reduction of redoxinert substrates including aryl, alkyl halides, azides, phosphate and ammonium salts (E red up to -2.83 vs SCE) under singl

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

It is typically read by researchers, students, and practitioners in Chemistry.

Author
Tommaso Bortolato; Gianluca Simionato; Marie Vayer; Cristian Rosso; Lorenzo Paoloni; Edmondo M. Benetti; Andrea Sartorel; David Lebœuf; Luca Dell’Amico
Publisher
American Chemical Society (ACS)
Published
2023
Language
EN
Field
Chemistry (Physical Sciences)