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–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-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 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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Bimetallic Porphyrin Metal–Organic Framework as Photocatalyst for Red-Light-Driven Selective Reduction of Nitroarenes to Aromatic Amines

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

It is a great challenge to construct green catalytic system for the reduction of nitro compounds corresponding amines under mild conditions. Due low energy red light, it challenging develop photocatalytic selective nitroaromatics aromatic driven by light. A bimetallic porphyrin metal–organic framework (Bi-P(Co)MOF) was characterized Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, scanning and energy-dispersive techniques. The constructed photocatalyst Bi-PMOF-Co shows excellent activity conversion in high yields with NaBH4 as reducing agent at room temperature light irradiation. Moreover, protocol showed functional group compatibility, recyclability demonstrated five-cycle tests.

Language: Английский

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Structurally Well-Defined PC(sp³)P Osmium Pincer Catalysts for Methylation of Alcohols, Indoles, Phenols, and Sulfonamides Using Methanol as a C₁ Source

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1629 - 1638

Published: Jan. 17, 2024

Recent findings show pincer catalysts of osmium superior in a broad spectrum synthetically valuable transformations. This article reports structurally well-defined Os(II)PCsp3P complexes stabilized by functional dibenzobarrelene-based ligand. We describe their organometallic and catalytic properties the hydride transfer reactions. demonstrate that center, covalently locked within 3-dimensional ligand pocket, exhibits strictly predictable coordination behavior redox rigidity while remaining catalytically active owing to potential cooperation with proximate side arm. The described were found as mild selective methylation alcohols, indoles, phenols, sulfonamides using methanol C1 source.

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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