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Voltage-driven control of single-molecule keto-enol equilibrium in a two-terminal junction system

Author

Listed:
  • Chun Tang

    (Xiamen University
    Southern University of Science and Technology)

  • Thijs Stuyver

    (Edmond J. Safra Campus at Givat Ram, The Hebrew University
    Ecole Nationale Supérieure de Chimie de Paris, Université PSL, CNRS, Institute of Chemistry for Life and Health Sciences)

  • Taige Lu

    (Xiamen University)

  • Junyang Liu

    (Xiamen University)

  • Yiling Ye

    (Xiamen University)

  • Tengyang Gao

    (Xiamen University)

  • Luchun Lin

    (Xiamen University)

  • Jueting Zheng

    (Xiamen University)

  • Wenqing Liu

    (Xiamen University)

  • Jia Shi

    (Xiamen University)

  • Sason Shaik

    (Edmond J. Safra Campus at Givat Ram, The Hebrew University)

  • Haiping Xia

    (Xiamen University
    Southern University of Science and Technology)

  • Wenjing Hong

    (Xiamen University)

Abstract

Keto-enol tautomerism, describing an equilibrium involving two tautomers with distinctive structures, provides a promising platform for modulating nanoscale charge transport. However, such equilibria are generally dominated by the keto form, while a high isomerization barrier limits the transformation to the enol form, suggesting a considerable challenge to control the tautomerism. Here, we achieve single-molecule control of a keto-enol equilibrium at room temperature by using a strategy that combines redox control and electric field modulation. Based on the control of charge injection in the single-molecule junction, we could access charged potential energy surfaces with opposite thermodynamic driving forces, i.e., exhibiting a preference for the conducting enol form, while the isomerization barrier is also significantly reduced. Thus, we could selectively obtain desired and stable tautomers, which leads to significant modulation of the single-molecule conductance. This work highlights the concept of single-molecule control of chemical reactions on more than one potential energy surface.

Suggested Citation

  • Chun Tang & Thijs Stuyver & Taige Lu & Junyang Liu & Yiling Ye & Tengyang Gao & Luchun Lin & Jueting Zheng & Wenqing Liu & Jia Shi & Sason Shaik & Haiping Xia & Wenjing Hong, 2023. "Voltage-driven control of single-molecule keto-enol equilibrium in a two-terminal junction system," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-39198-7
    DOI: 10.1038/s41467-023-39198-7
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    References listed on IDEAS

    as
    1. Yaping Zang & Qi Zou & Tianren Fu & Fay Ng & Brandon Fowler & Jingjing Yang & Hexing Li & Michael L. Steigerwald & Colin Nuckolls & Latha Venkataraman, 2019. "Directing isomerization reactions of cumulenes with electric fields," Nature Communications, Nature, vol. 10(1), pages 1-7, December.
    2. Ce Zhou & Xingxing Li & Zhongliang Gong & Chuancheng Jia & Yuanwei Lin & Chunhui Gu & Gen He & Yuwu Zhong & Jinlong Yang & Xuefeng Guo, 2018. "Direct observation of single-molecule hydrogen-bond dynamics with single-bond resolution," Nature Communications, Nature, vol. 9(1), pages 1-9, December.
    3. Latha Venkataraman & Jennifer E. Klare & Colin Nuckolls & Mark S. Hybertsen & Michael L. Steigerwald, 2006. "Dependence of single-molecule junction conductance on molecular conformation," Nature, Nature, vol. 442(7105), pages 904-907, August.
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