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Ag3PO4 enables the generation of long-lived radical cations for visible light-driven [2 + 2] and [4 + 2] pericyclic reactions

Author

Listed:
  • Lirong Guo

    (School of Chemistry and Chemical Engineering Shandong University Jinan)

  • Rongchen Chu

    (School of Chemistry and Chemical Engineering Shandong University Jinan)

  • Xinyu Hao

    (School of Chemistry and Chemical Engineering Shandong University Jinan)

  • Yu Lei

    (Institute of Chemistry Chinese Academy of Sciences Beijing)

  • Haibin Li

    (School of Chemistry and Chemical Engineering Shandong University Jinan)

  • Dongge Ma

    (College of Chemistry and Materials Engineering Beijing Technology and Business University Beijing)

  • Guo Wang

    (Department of Chemistry Capital Normal University Beijing)

  • Chen-Ho Tung

    (School of Chemistry and Chemical Engineering Shandong University Jinan)

  • Yifeng Wang

    (School of Chemistry and Chemical Engineering Shandong University Jinan)

Abstract

Photocatalytic redox reactions are important for synthesizing fine chemicals from olefins, but the limited lifetime of radical cation intermediates severely restricts semiconductor photocatalysis efficiency. Here, we report that Ag3PO4 can efficiently catalyze intramolecular and intermolecular [2 + 2] and Diels-Alder cycloadditions under visible-light irradiation. The approach is additive-free, catalyst-recyclable. Mechanistic studies indicate that visible-light irradiation on Ag3PO4 generates holes with high oxidation power, which oxidize aromatic alkene adsorbates into radical cations. In photoreduced Ag3PO4, the conduction band electron (eCB−) has low reduction power due to the delocalization among the Ag+-lattices, while the particle surfaces have a strong electrostatic interaction with the radical cations, which considerably stabilize the radical cations against recombination with eCB−. The radical cation on the particle’s surfaces has a lifetime of more than 2 ms, 75 times longer than homogeneous systems. Our findings highlight the effectiveness of inorganic semiconductors for challenging radical cation-mediated synthesis driven by sunlight.

Suggested Citation

  • Lirong Guo & Rongchen Chu & Xinyu Hao & Yu Lei & Haibin Li & Dongge Ma & Guo Wang & Chen-Ho Tung & Yifeng Wang, 2024. "Ag3PO4 enables the generation of long-lived radical cations for visible light-driven [2 + 2] and [4 + 2] pericyclic reactions," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-45217-y
    DOI: 10.1038/s41467-024-45217-y
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    References listed on IDEAS

    as
    1. Can Yang & Run Li & Kai A. I. Zhang & Wei Lin & Katharina Landfester & Xinchen Wang, 2020. "Heterogeneous photoredox flow chemistry for the scalable organosynthesis of fine chemicals," Nature Communications, Nature, vol. 11(1), pages 1-8, December.
    2. Jingwen Ke & Jiankang Zhao & Mingfang Chi & Menglin Wang & Xiangdong Kong & Qixuan Chang & Weiran Zhou & Chengxuan Long & Jie Zeng & Zhigang Geng, 2022. "Facet-dependent electrooxidation of propylene into propylene oxide over Ag3PO4 crystals," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
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