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

被引:26
作者
Bortolato, Tommaso [1 ]
Simionato, Gianluca [1 ]
Vayer, Marie [2 ]
Rosso, Cristian [1 ]
Paoloni, Lorenzo [3 ]
Benetti, Edmondo M. [1 ]
Sartorel, Andrea [1 ]
Leboeuf, David [2 ]
Dell'Amico, Luca [1 ]
机构
[1] Univ Padua, Dept Chem Sci, I-35131 Padua, Italy
[2] Univ Strasbourg, Inst Sci & Ingn Supramol ISIS, CNRS UMR 7006, F-67000 Strasbourg, France
[3] Univ Padua, Dipartimento Fisicae Astron G Galilei, I-35131 Padua, Italy
基金
欧洲研究理事会;
关键词
LIGHT PHOTOREDOX CATALYSIS; DEEP BLUE; EFFICIENCY; REDUCTION; DRIVEN; OLEDS; DYES;
D O I
10.1021/jacs.2c11364
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Photocatalysis has become a prominent tool in the arsenal of organic chemists to develop and (re)imagine trans-formations. However, only a handful of versatile organic photo-catalysts (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 D, 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 redox-inert substrates including aryl, alkyl halides, azides, phosphate and ammonium salts (Ered up to -2.83 vs SCE) under single-photon excitation. We anticipate that these new PCs will open new mechanistic manifolds in the field of photocatalysis by allowing access to previously inaccessible radical intermediates under one-photon excitation.
引用
收藏
页码:1835 / 1846
页数:12
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