CdS Quantum Dots as Potent Photoreductants for Organic Chemistry Enabled by Auger Processes

Strong reducing agents (

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Veröffentlicht in:Journal of the American Chemical Society 2022-07, Vol.144 (27), p.12229-12246
Hauptverfasser: Widness, Jonas K., Enny, Daniel G., McFarlane-Connelly, Kaelyn S., Miedenbauer, Mahilet T., Krauss, Todd D., Weix, Daniel J.
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container_end_page 12246
container_issue 27
container_start_page 12229
container_title Journal of the American Chemical Society
container_volume 144
creator Widness, Jonas K.
Enny, Daniel G.
McFarlane-Connelly, Kaelyn S.
Miedenbauer, Mahilet T.
Krauss, Todd D.
Weix, Daniel J.
description Strong reducing agents (
doi_str_mv 10.1021/jacs.2c03235
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Stoichiometric metallic reductants such as alkali metals and SmI2 are commonly employed for these reactions; however, considerations including expense, ease of use, safety, and waste generation limit the practicality of these methods. Recent approaches utilizing energy from multiple photons or electron-primed photoredox catalysis have accessed reduction potentials equivalent to Li0 and shown how this enables selective transformations of aryl chlorides via aryl radicals. However, in some cases, low stability of catalytic intermediates can limit turnover numbers. Herein, we report the ability of CdS nanocrystal quantum dots (QDs) to function as strong photoreductants and present evidence that a highly reducing electron is generated from two consecutive photoexcitations of CdS QDs with intermediate reductive quenching. Mechanistic experiments suggest that Auger recombination, a photophysical phenomenon known to occur in photoexcited anionic QDs, generates transient thermally excited electrons to enable the observed reductions. Using blue light-emitting diodes (LEDs) and sacrificial amine reductants, aryl chlorides and phosphate esters with reduction potentials up to −3.4 V vs SCE are photoreductively cleaved to afford hydrodefunctionalized or functionalized products. In contrast to small-molecule catalysts, QDs are stable under these conditions and turnover numbers up to 47 500 have been achieved. 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Herein, we report the ability of CdS nanocrystal quantum dots (QDs) to function as strong photoreductants and present evidence that a highly reducing electron is generated from two consecutive photoexcitations of CdS QDs with intermediate reductive quenching. Mechanistic experiments suggest that Auger recombination, a photophysical phenomenon known to occur in photoexcited anionic QDs, generates transient thermally excited electrons to enable the observed reductions. Using blue light-emitting diodes (LEDs) and sacrificial amine reductants, aryl chlorides and phosphate esters with reduction potentials up to −3.4 V vs SCE are photoreductively cleaved to afford hydrodefunctionalized or functionalized products. In contrast to small-molecule catalysts, QDs are stable under these conditions and turnover numbers up to 47 500 have been achieved. 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subjects Catalysis
Chemistry, Organic
Electrons
Quantum Dots - chemistry
Reducing Agents
title CdS Quantum Dots as Potent Photoreductants for Organic Chemistry Enabled by Auger Processes
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