High Triplet Energy Iridium(III) Isocyanoborato Complex for Photochemical Upconversion, Photoredox and Energy Transfer Catalysis DOI Creative Commons
Lucius Schmid, Felix Glaser,

Raoul S. Schaer

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(2), P. 963 - 976

Published: Jan. 5, 2022

Cyclometalated Ir(III) complexes are often chosen as catalysts for challenging photoredox and triplet-triplet-energy-transfer (TTET) catalyzed reactions, they of interest upconversion into the ultraviolet spectral range. However, triplet energies commonly employed photosensitizers typically limited to values around 2.5-2.75 eV. Here, we report on a new luminophore, with an unusually high energy near 3.0 eV owing modification previously reported complex isocyanoborato ligands. Compared nonborylated cyanido precursor complex, introduction B(C6F5)3 units in second coordination sphere results substantially improved photophysical properties, particular luminescence quantum yield (0.87) long excited-state lifetime (13.0 μs), addition energy. These favorable properties (including good long-term photostability) facilitate exceptionally organic photoreactions (sensitized) triplet-triplet annihilation fluorescent singlet excited state beyond 4 eV, deep region. The photocatalyzes sigmatropic shift [2 + 2] cycloaddition reactions that unattainable common transition metal-based photosensitizers. In presence sacrificial electron donor, it furthermore is applicable demanding photoreductions, including dehalogenations, detosylations, degradation lignin model substrate. Our study demonstrates how rational ligand design transition-metal underexplored effects) can be used enhance their thereby broaden application potential solar conversion synthetic photochemistry.

Language: Английский

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis DOI Creative Commons
Rens Ham, C. Jasslie Nielsen,

Sonja Pullen

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5225 - 5261

Published: Jan. 20, 2023

Because sunlight is the most abundant energy source on earth, it has huge potential for practical applications ranging from sustainable supply to light driven chemistry. From a chemical perspective, excited states generated by make thermodynamically uphill reactions possible, which forms basis storage into fuels. In addition, with light, open-shell species can be open up new reaction pathways in organic synthesis. Crucial are photosensitizers, absorb and transfer substrates various mechanisms, processes that highly depend distance between molecules involved. Supramolecular coordination cages well studied synthetically accessible vessels single cavities guest binding, ensuring close proximity of different components. Due high modularity their size, shape, nature metal centers ligands, ideal platforms exploit preorganization photocatalysis. Herein we focus application supramolecular photocatalysis artificial photosynthesis photo(redox) catalysis. Finally, brief overview immobilization strategies provides tools implementing devices. This review inspiration future design photocatalytic host-guest systems producing solar fuels complex molecules.

Language: Английский

Citations

169
Energy transfer photocatalysis: exciting modes of reactivity DOI
Subhabrata Dutta, Johannes E. Erchinger, Felix Strieth‐Kalthoff

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(3), P. 1068 - 1089

Published: Jan. 1, 2024

Leveraging light energy to expose the ‘dark’ reactive states describes whole essence of triplet–triplet transfer. This offers an impressive opportunity conduct a multitude diverse reactions and access sought-after molecular motifs.

Language: Английский

Citations

136
Switchable Divergent Synthesis Using Photocatalysis DOI
Yota Sakakibara, Kei Murakami

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(3), P. 1857 - 1878

Published: Jan. 20, 2022

A highly selective and divergent synthesis enables access to various molecules has garnered broad interest from not only organic chemists but also medicinal biologists who work with chemical libraries. Since the 20th century, such transformations have been achieved using transition-metal-catalyzed reactions, in which choice of catalyst or ligand crucially affects selectivity. Over past several decades, photocatalysts attracted a considerable amount attention because they provide additional ways control reaction intermediates product selectivity via electron energy transfer. From this perspective, we highlight recent development switchable syntheses photocatalysts, are difficult achieve classical catalytic transformations.

Language: Английский

Citations

114
Light-empowered contra-thermodynamic stereochemical editing DOI

Peng‐Zi Wang,

Wen‐Jing Xiao, Jia‐Rong Chen

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 7(1), P. 35 - 50

Published: Nov. 16, 2022

Language: Английский

Citations

78
Synthesis of Cyclopropenols Enabled by Visible‐Light‐Induced Organocatalyzed [2+1] Cyclization DOI
Gang Zhou, Xiao Shen

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(10)

Published: Jan. 7, 2022

Although the synthesis of common cyclopropenes has been well studied, access to cyclopropenols is rather limited. Herein, we report first α-trifluoromethylated via 2+1 cycloaddition reactions between alkynes and trifluoroacylsilanes, enabled by visible-light-induced organocatalysis. The novel ambiphilic donor-acceptor carbenes derived from trifluoroacetylsilanes reacted efficiently with both activated non-activated alkynes. reaction features simple operation, mild conditions, broad substrate scope good functional group tolerance. synthetic potential highlighted gram-scale cyclopropanols through combination cyclization high diastereoselective hydrogenation in one pot.

Language: Английский

Citations

74
Light-enabled deracemization of cyclopropanes by Al-salen photocatalysis DOI Creative Commons

Carina Onneken,

Tobias Morack,

Julia Soika

et al.

Nature, Journal Year: 2023, Volume and Issue: 621(7980), P. 753 - 759

Published: Aug. 23, 2023

Privileged chiral catalysts-those that share common structural features and are enantioselective across a range of reactions-continue to transform the chemical-research landscape1. In recent years, new reactivity modes have been achieved through excited-state catalysis, processes activated by light, but it is unclear if selectivity ground-state privileged catalysts can be matched. Although interception photogenerated intermediates cycles has partially addressed this challenge2, single, photocatalysts simultaneously regulate conspicuously scarce3. So far, precision donor-acceptor recognition motifs remain crucial in photocatalyst design4. Here we show Al-salen complexes, which well-defined photophysical properties, used for efficient photochemical deracemization5 cyclopropyl ketones (up 98:2 enantiomeric ratio (e.r.)). Irradiation at λ = 400 nm (violet light) augments commercial catalyst enable enantioselectivity regulated simultaneously. This circumvents need tailored catalyst-substrate motifs. It predicted study will stimulate re-evaluation many venerable (ground-state) processes, ultimately leading identification candidates may considered 'privileged' both models.

Language: Английский

Citations

63
Near‐Infrared Light‐Driven Photocatalysis with an Emphasis on Two‐Photon Excitation: Concepts, Materials, and Applications DOI Creative Commons
Chuang Han, Bidyut Kumar Kundu, Yujun Liang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(5)

Published: Sept. 13, 2023

Efficient utilization of sunlight in photocatalysis is widely recognized as a promising solution for addressing the growing energy demand and environmental issues resulting from fossil fuel consumption. Recently, there have been significant developments various near-infrared (NIR) light-harvesting systems artificial photosynthesis photocatalytic remediation. This review provides an overview most recent advancements NIR light through creation novel nanostructured materials molecular photosensitizers, well modulating strategies to enhance processes. A special focus given emerging two-photon excitation photocatalysis. The unique features limitations different are critically evaluated. In particular, it highlights advantages utilizing compared UV-visible irradiation one-photon excitation. Ongoing challenges potential solutions future exploration light-responsive also discussed.

Language: Английский

Citations

54
The impact of UV light on synthetic photochemistry and photocatalysis DOI
Giulio Goti, Kavyasree Manal, Jayaraman Sivaguru

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(5), P. 684 - 692

Published: March 1, 2024

Language: Английский

Citations

40
Single-Electron Oxidation-Initiated Enantioselective Hydrosulfonylation of Olefins Enabled by Photoenzymatic Catalysis DOI

Qinglong Shi,

Xiu‐Wen Kang, Zhiyong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2748 - 2756

Published: Jan. 12, 2024

Controlling the enantioselectivity of hydrogen atom transfer (HAT) reactions has been a long-standing synthetic challenge. While recent advances on photoenzymatic catalysis have demonstrated great potential non-natural photoenzymes, all transformations are initiated by single-electron reduction substrate, with only one notable exception. Herein, we report an oxidation-initiated enantioselective hydrosulfonylation olefins using novel mutant gluconobacter ene-reductase (GluER-W100F-W342F). Compared to known systems, our approach does not rely formation electron donor–acceptor complex between substrates and enzyme cofactor simplifies reaction system obviating addition regeneration mixture. More importantly, GluER variant exhibits high reactivity broad substrate scope. Mechanistic studies support proposed mechanism reveal that tyrosine-mediated HAT process is involved.

Language: Английский

Citations

36
Chiral arylsulfinylamides as reagents for visible light-mediated asymmetric alkene aminoarylations DOI Creative Commons
Cédric Hervieu, Mariia S. Kirillova, Yawen Hu

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 607 - 614

Published: Jan. 16, 2024

Abstract Two- or one-electron-mediated difunctionalizations of internal alkenes represent straightforward approaches to assemble molecular complexity by the simultaneous formation two contiguous C sp 3 stereocentres. Although racemic versions have been extensively explored, asymmetric variants, especially those involving open-shell C-centred radical species, are much more limited both in number and scope. Here we describe enantioenriched arylsulfinylamides as all-in-one reagents for efficient asymmetric, intermolecular aminoarylation alkenes. Under mild photoredox conditions, nitrogen addition arylsulfinylamide onto double bond, followed 1,4-translocation aromatic ring, produce, a single operation, corresponding adducts enantiomerically enriched form. The sulfinyl group acts here traceless chiral auxiliary, it is eliminated situ under reaction conditions. Optically pure β,β-diarylethylamines, aryl-α,β-ethylenediamines α-aryl-β-aminoalcohols, prominent motifs pharmaceuticals, bioactive natural products ligands transition metals, thereby accessible with excellent levels regio-, relative absolute stereocontrol.

Language: Английский

Citations

34