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Universal inter-molecular radical transfer reactions on metal surfaces

Author

Listed:
  • Junbo Wang

    (Shaanxi Normal University
    Soochow University)

  • Kaifeng Niu

    (Soochow University
    Linköping University)

  • Huaming Zhu

    (Shaanxi Normal University)

  • Chaojie Xu

    (Soochow University)

  • Chuan Deng

    (Shaanxi Normal University)

  • Wenchao Zhao

    (James-Franck-Str. 1)

  • Peipei Huang

    (Shaanxi Normal University)

  • Haiping Lin

    (Shaanxi Normal University)

  • Dengyuan Li

    (East China University of Science & Technology)

  • Johanna Rosen

    (Linköping University)

  • Peinian Liu

    (East China University of Science & Technology)

  • Francesco Allegretti

    (James-Franck-Str. 1)

  • Johannes V. Barth

    (James-Franck-Str. 1)

  • Biao Yang

    (Soochow University
    James-Franck-Str. 1)

  • Jonas Björk

    (Linköping University)

  • Qing Li

    (Shaanxi Normal University)

  • Lifeng Chi

    (Soochow University
    Macau University of Science and Technology)

Abstract

On-surface synthesis provides tools to prepare low-dimensional supramolecular structures. Traditionally, reactive radicals are a class of single-electron species, serving as exceptional electron-withdrawing groups. On metal surfaces, however, such species are affected by conduction band screening effects that may even quench their unpaired electron characteristics. As a result, radicals are expected to be less active, and reactions catalyzed by surface-stabilized radicals are rarely reported. Herein, we describe a class of inter-molecular radical transfer reactions on metal surfaces. With the assistance of aryl halide precursors, the coupling of terminal alkynes is steered from non-dehydrogenated to dehydrogenated products, resulting in alkynyl-Ag-alkynyl bonds. Dehalogenated molecules are fully passivated by detached hydrogen atoms. The reaction mechanism is unraveled by various surface-sensitive technologies and density functional theory calculations. Moreover, we reveal the universality of this mechanism on metal surfaces. Our studies enrich the on-surface synthesis toolbox and develop a pathway for producing low-dimensional organic materials.

Suggested Citation

  • Junbo Wang & Kaifeng Niu & Huaming Zhu & Chaojie Xu & Chuan Deng & Wenchao Zhao & Peipei Huang & Haiping Lin & Dengyuan Li & Johanna Rosen & Peinian Liu & Francesco Allegretti & Johannes V. Barth & Bi, 2024. "Universal inter-molecular radical transfer reactions on metal surfaces," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-47252-1
    DOI: 10.1038/s41467-024-47252-1
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    References listed on IDEAS

    as
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