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

JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 2746 - 2766

Published: Aug. 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

Language: Английский

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Red-Light-Active N,C,N-Pincer Bismuthinidene: Excited State Dynamics and Mechanism of Oxidative Addition into Aryl Iodides

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Despite the progress made in field of synthetic organic photocatalysis over past decade, use higher wavelengths, especially those deep-red portion electromagnetic spectrum, remains comparatively rare. We have previously disclosed that a well-defined N,C,N-pincer bismuthinidene (1a) can undergo formal oxidative addition into wide range aryl electrophiles upon absorption low-energy red light. In this study, we map out photophysical dynamics 1a and glean insights nature excited state responsible for activation electrophiles. Transient emission techniques reveal that, irradiation with light, complex undergoes direct S0 → S1 metal-to-ligand charge transfer (MLCT) transition, followed by rapid intersystem crossing (ISC) to highly reducing emissive triplet (−2.61 V vs Fc+/0 MeCN). The low dissipative losses incurred during ISC (∼6% incident light energy) help rationalize ability convert useful chemical energy. Spectroelectrochemical computational data support charge-separated excited-state structure radical-anion character on ligand radical-cation bismuth. Kinetic studies competition experiments afford mechanism iodides; concerted inner-sphere processes from are ruled out, strongly supporting pathway proceeds via outer-sphere dissociative electron transfer.

Language: Английский

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Red Light–Blue Light Chromoselective C(sp²)–X Bond Activation by Organic Helicenium-Based Photocatalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7922 - 7930

Published: March 18, 2024

Chromoselective bond activation has been achieved in organic helicenium (nPr-DMQA+)-based photoredox catalysis. Consequently, control over chromoselective C(sp2)–X multihalogenated aromatics demonstrated. nPr-DMQA+ can only initiate the halogen atom transfer (XAT) pathway under red light irradiation to activate low-energy-accessible C(sp2)–I bonds. In contrast, blue initiates consecutive photoinduced electron (conPET) more challenging C(sp2)–Br Comparative reaction outcomes have demonstrated α-arylation of cyclic ketones with and lights. Furthermore, red-light-mediated selective bonds activated iodobromoarenes keep bromo functional handle untouched. Finally, strength catalysis highlighted two-fold functionalization using both photo-to-transition metal photo-to-photocatalyzed transformations.

Language: Английский

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Red-Light Mediated Formylation of Indoles Using Helical Carbenium Ion as Photoredox Catalyst

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A red-light ( λ = 640 nm)-mediated C-3 formylation of indoles utilizing a helical carbenium ion as photocatalyst and 2,2-dimethoxy- N , -dimethylethanamine formylating source is presented.

Language: Английский

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Synthesis, Characterization, and Catalytic Activity of Ni(0) (DQ)dtbbpy, an Air-Stable, Bifunctional Red-Light-Sensitive Precatalyst

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Despite a well-established and growing body of work on nickel(0) precatalysts, the potential complexes as bifunctional precatalysts remains underexplored. In this study, we synthesized, characterized, evaluated catalytic activity (Ni(0)(DQ)dtbbpy), bifunctional, red-light-sensitive, air-stable complex. Owing to its unique photophysical properties, it effectively catalyzed etherification amination aryl bromides under 620–630 nm light irradiation, functioning both photocatalyst an active metal catalyst. Mechanistic studies density functional theory (DFT) calculations further confirmed exceptional absorption properties Ni(0)(DQ)dtbbpy in red-light region, well electron transfer process triggered by irradiation.

Language: Английский

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Recent Advances in Photoredox-Catalyzed Difunctionalization of Alkenes

Catalysts, Journal Year: 2023, Volume and Issue: 13(7), P. 1056 - 1056

Published: June 30, 2023

Alkenes and their related analogs are ideal starting materials for organic synthesis, the selective difunctionalization of alkenes, which allows simultaneous introduction two neighboring bonds, has gained considerable attention in recent years. In particular, photoredox-catalyzed alkenes also been accomplished, regarded as an increasingly powerful tool synthesis miscellaneous interesting molecular scaffolds environmentally benign economical manner. Several exquisite strategies have developed to facilitate this transformation, such photosensitizer-catalyzed redox reactions, electron donor-acceptor (EDA) complexes-mediated photoreactions, atom transfer radical addition (ATRA) reactions. This literature review briefly describes most key progress on 1,2-difunctionalization various structurally diverse including 1,2-dicarbofunctionalization, 1,2-carboheterofunctionalization, 1,2-diheterofunctionalization, with a special emphasis mechanistic details.

Language: Английский

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Orange Light-Driven C(sp²)–C(sp³) Cross-Coupling via Spin-Forbidden Ir(III) Metallaphotoredox Catalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19925 - 19931

Published: Aug. 29, 2023

We report the development and characterization of a library Ir(III) photocatalysts capable undergoing spin-forbidden excitation (SFE) under orange light irradiation (595 nm). These catalysts were successfully applied to construction synthetically valuable C(sp2)-C(sp3) bonds inaccessible with existing methods low-energy light-driven dual nickel/photoredox catalysis, demonstrating synthetic utility this photocatalyst family. The are accessing both oxidatively reductively activated coupling partners, illustrated through deaminative arylation potassium alkyl trifluoroborate cross-coupling reactions aryl halides. demonstrate diverse substrate scopes paradigms mild conditions in first example metallaphotoredox coupling.

Language: Английский

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Nitrative Difunctionalization of Alkenes via Cobalt-Mediated Radical Ligand Transfer and Radical-Polar Crossover Photoredox Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16136 - 16147

Published: Dec. 1, 2023

Herein, we report the rational design of a modular dual photoredox and cobalt catalysis paradigm for difunctionalization unsaturated hydrocarbons, unlocking synthesis valuable but challenging 1,2-halonitroalkane substrate class. The protocol relies on use redox-active organic nitrating reagent N-nitrosuccinimide as source nitryl radicals cobalt-mediated radical ligand transfer (RLT) methodology to form carbon–halogen bond. This synergistic cooperation between photocatalyst high-valence metal center occurs under mild reaction conditions is capable delivering 1,2-chloronitro- 1,2-bromonitroalkanes in single chemical operation while exhibiting high functional-group tolerance exclusive regioselectivity variety olefins. Mechanistic studies based both experimental spectroscopic analysis provided insights into nature this catalytic halo-nitration process including evidence halogen catalyst. Furthermore, employing net-neutral radical/polar crossover (RPC) approach cobalt-free allowed us accommodate external protic nucleophiles, thiols, alcohols, acids, and, notably, substituted amines. Highly functionalized olefin scaffolds also successfully underwent nitrative difunctionalization, demonstrating viability these protocols late-stage functionalization bioactive molecules.

Language: Английский

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Recent advancements in the molecular design of deep-red to near-infrared light-absorbing photocatalysts

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(8), P. 100973 - 100973

Published: April 17, 2024

Language: Английский

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Red-Light-Promoted Radical Cascade Reaction to Access Tetralins and Dialins Enabled by Zinc(II)porphyrin, A Light-Flexible Catalyst

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3929 - 3934

Published: April 26, 2024

[5,15-Bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II) (1), a metalloporphyrin derivative that was recently reported as an efficient photocatalyst driven by blue LEDs our group, found to catalyze red-light-promoted (630 nm LEDs) radical cascade reaction of N-3-arylpropionyloxyphthalimides with radicophiles including electron-deficient alkenes and alkynes, providing access range functionalized tetralin dialin derivatives. The catalyzed 1 took place via oxidative quenching cycle in DMSO, where no sacrificial electron donor required, uncovering unique solvent effect capable promoting the porphyrin catalysis.

Language: Английский

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