NIR-II emissive anionic copper nanoclusters with intrinsic photoredox activity in single-electron transfer

Li-Juan Liu, Mao-Mao Zhang, Ziqi Deng, Liang-Liang Yan, Yang Lin, David Lee Phillips, Vivian Wing-Wah Yam and Jian He ()
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Li-Juan Liu: The University of Hong Kong
Mao-Mao Zhang: The University of Hong Kong
Ziqi Deng: The University of Hong Kong
Liang-Liang Yan: The University of Hong Kong
Yang Lin: The University of Hong Kong
David Lee Phillips: The University of Hong Kong
Vivian Wing-Wah Yam: The University of Hong Kong
Jian He: The University of Hong Kong

Nature Communications, 2024, vol. 15, issue 1, 1-12

Abstract: Abstract Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas for efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of organic transformations that copper nanoclusters can catalyze remain limited to date. Herein, we report a structurally well-defined anionic Cu40 nanocluster that emits in the second near-infrared region (NIR-II, 1000−1700 nm) after photoexcitation and can conduct single-electron transfer with fluoroalkyl iodides without the need for external ligand activation. This photoredox-active copper nanocluster efficiently catalyzes the three-component radical couplings of alkenes, fluoroalkyl iodides, and trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety of fluorine-containing electrophiles and a cyanide nucleophile can be added onto an array of alkenes, including styrenes and aliphatic olefins. Our current work demonstrates the viability of using readily accessible metal nanoclusters to establish photocatalytic systems with a high degree of practicality and reaction complexity.

Date: 2024
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DOI: 10.1038/s41467-024-49081-8

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