Challenges and Future Perspectives in Photocatalysis: Conclusions from an Interdisciplinary Workshop

JACS Au, Год журнала: 2024, Номер 4(8), С. 2746 - 2766

Опубликована: Авг. 8, 2024

Photocatalysis is a versatile and rapidly developing field with applications spanning artificial photosynthesis, photo-biocatalysis, photoredox catalysis in solution or supramolecular structures, utilization of abundant metals organocatalysts, sustainable synthesis, plastic degradation. In this Perspective, we summarize conclusions from an interdisciplinary workshop young principal investigators held at the Lorentz Center Leiden March 2023. We explore how diverse fields within photocatalysis can benefit one another. delve into intricate interplay between these subdisciplines, by highlighting unique challenges opportunities presented each multidisciplinary approach drive innovation lead to solutions for future. Advanced collaboration knowledge exchange across domains further enhance potential photocatalysis. Artificial photosynthesis has become promising technology solar fuel generation, instance, via water splitting CO

Язык: Английский

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Excited Organic Radicals in Photoredox Catalysis

JACS Au, Год журнала: 2025, Номер 5(2), С. 426 - 447

Опубликована: Янв. 29, 2025

Many important synthetic-oriented works have proposed excited organic radicals as photoactive species, yet mechanistic studies raised doubts about whether they can truly function photocatalysts. This skepticism originates from the formation of (photo)redox-active degradation products and picosecond decay electronically radicals, which is considered too short for diffusion-based photoinduced electron transfer reactions. From this perspective, we analyze synthetic transformations where been photocatalysts, comparing their theoretical maximum state potentials with required observed photocatalytic reactivity. We summarize structurally similar photocatalysts indicating different reaction pathways some catalytic systems, addressing cases radical exceed Additionally, perform a kinetic analysis to explain in on subpicosecond time scales. further rationalize potential anti-Kasha reactivity higher states femtosecond lifetimes, highlighting how future photocatalysis advancements could unlock new photochemical pathways.

Язык: Английский

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Photo- and electro-chemical strategies for the activations of strong chemical bonds

Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 263 - 316

Опубликована: Дек. 7, 2023

The employment of light and/or electricity - alternatively to conventional thermal energy unlocks new reactivity paradigms as tools for chemical substrate activations. This leads the development synthetic reactions and a vast expansion spaces. review summarizes recent developments in photo- electrochemical activation strategies functionalization strong bonds particularly carbon-heteroatom (C-X)

Язык: Английский

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Ketyl Radical Coupling Enabled by Polycyclic Aromatic Hydrocarbon Electrophotocatalysts

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(37), С. 20169 - 20175

Опубликована: Сен. 7, 2023

Herein, we report a new class of electrophotocatalysts, polycyclic aromatic hydrocarbons, that promote the reduction unactivated carbonyl compounds to generate versatile ketyl radical intermediates. This catalytic platform enables previously challenging intermolecular coupling reactions, including those classic reductants (e.g., SmI2/HMPA) have failed promote. More broadly, this study outlines an approach fundamentally expand array reactive intermediates can be generated via electrophotocatalysis by obviating need for rapid mesolytic cleavage following substrate reduction.

Язык: Английский

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Electron‐Poor Acridones and Acridiniums as Super Photooxidants in Molecular Photoelectrochemistry by Unusual Mechanisms

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Авг. 16, 2023

Abstract Electron‐deficient acridones and in situ generated acridinium salts are reported as potent, closed‐shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open‐shell, radical cationic, ‘beyond diffusion’ photocatalysis to closed‐shell, neutral, diffusion‐controlled photocatalysis. Brønsted acid activation of dramatically increases excited state oxidation power (by +0.8 V). Upon reduction protonated acridones, they transform electron‐deficient even more potent (* E 1/2 =+2.56–3.05 V vs SCE). These oxidize arenes where conventional salt have thusfar been limited electron‐rich arenes. Surprisingly, upon photoexcitation these appear two electron reductive quenching form acridinide anions, spectroscopically‐detected forms. This new behaviour is partly enabled by catalyst preassembly the arene, contrasts SET salts. Critically, study illustrates how redox active chromophoric molecules initially considered photocatalysts can during reaction catalytically species different spectroscopic properties.

Язык: Английский

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Electrophotocatalytic hydrogenation of imines and reductive functionalization of aryl halides

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 22, 2024

Abstract The open-shell catalytically active species, like radical cations or anions, generated by one-electron transfer of precatalysts are widely used in energy-consuming redox reactions, but their excited-state lifetimes usually short. Here, a closed-shell thioxanthone-hydrogen anion species ( 3 ), which can be photochemically converted to potent and long-lived reductant, is under electrochemical conditions, enabling the electrophotocatalytic hydrogenation. Notably, TfOH regulate potential this system. In presence TfOH, precatalyst 1 ) reduction occur at low potential, so that competitive H 2 evolution inhibited, thus effectively promoting hydrogenation imines. absence reducing ability system reach potency even comparable Na 0 Li , thereby allowing hydrogenation, borylation, stannylation (hetero)arylation aryl halides construct C−H, C−B, C−Sn, C−C bonds.

Язык: Английский

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Electrophotocatalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2024, Номер 124(21), С. 12264 - 12304

Опубликована: Окт. 23, 2024

Electrocatalysis and photocatalysis have been the focus of extensive research efforts in organic synthesis recent decades, these powerful strategies provided a wealth new methods to construct complex molecules. Despite intense efforts, only recently has there significant on combined use two modalities. Nevertheless, past five years witnessed rapidly growing interest area electrophotocatalysis. This hybrid strategy capitalizes enormous benefits using photons as reagents while also employing an electric potential convenient tunable source or sink electrons. Research this topic led number for C-H functionalization, reductive cross-coupling, olefin addition among others. field seen broad range catalyst types, including both metal organocatalysts. Of particular note work with open-shell photocatalysts, which tend comparatively large redox potentials. Electrochemistry provides means generate such species, making electrophotocatalysis particularly amenable intriguing class catalyst. review surveys applied synthesis, organized broadly into oxidative, reductive, neutral transformations.

Язык: Английский

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Making Mo(0) a Competitive Alternative to Ir(III) in Phosphors and Photocatalysts

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Iridium is used in commercial light-emitting devices and photocatalysis but among the rarest stable chemical elements. Therefore, replacing iridium(III) photoactive molecular complexes with abundant metals of great interest. First-row transition generally tend to yield poorer luminescence behavior, it remains difficult obtain excited states redox properties that exceed those noble-metal-based photocatalysts. Here, we overcome these challenges a nonprecious second-row metal. Tailored coordination spheres for molybdenum(0) lead photoluminescence quantum yields rival photochemical reduction reactions not normally achievable become possible. These developments open new perspectives noble lighting applications Earth-abundant advancing metal-based beyond current limits.

Язык: Английский

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Throwing Light on Synthetic Molecular Photoelectrocatalysis (Part I): coupling both techniques and results interpretation

Current Opinion in Electrochemistry, Год журнала: 2025, Номер unknown, С. 101673 - 101673

Опубликована: Фев. 1, 2025

Язык: Английский

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Modern photo- and electrochemical approaches to aryl radical generation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(18), С. 5232 - 5277

Опубликована: Янв. 1, 2024

This review describes recent advances in the generation of aryl radicals using light and electricity. Such modern techniques allow for efficient energy resource utilization, thus providing more sustainable radical arylation methods.

Язык: Английский

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