Force-driven single-molecule transformations through tip-mediated stabilization of transition states

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Abstract
Mechanochemistry uses mechanical forces to drive chemical transformations, offering an energy-efficient alternative to traditional thermal, optical, or electrical reaction pathways. At the single-molecule scale, controlling structural changes with mechanical stimuli is fundamental for developing nanoscale devices and understanding chemical reactivity. In conventional single-molecule reactions driven by light or electrical currents, energy is supplied through one-way excitation processes, requiring the single-event energy input to exceed the activation energy barrier. Here we show that mechanically driven single-molecule reactions can bypass this limitation, proceeding with a net energy cost below the activation energy. By using atomic force microscopy to induce the structural inversion of individual, bowl-shaped sumanene molecules on a gold surface, we measure the mechanical energy spent during the transformation. The net energy cost is significantly lower than the theoretical activation energy. This sub-barrier reaction occurs because attractive van der Waals forces from the mesoscopic tip body stabilize the transition state more effectively than the final state. Our findings demonstrate a distinct energetic mechanism in mechanochemistry, highlighting alternative strategies for energy-efficient molecular manipulation.
Funding Information
  • Japan Society for the Promotion of Science (25K22215)
  • Japan Society for the Promotion of Science (26K01386)
  • Japan Society for the Promotion of Science (26H01330)
  • Japan Society for the Promotion of Science (24H01175)
  • Japan Society for the Promotion of Science (23K13665)
  • Japan Society for the Promotion of Science (JP21H05233)
  • Japan Society for the Promotion of Science (24H00460)
  • Japan Science and Technology Agency (JPMJFR203J)
  • Nippon Sheet Glass Foundation for Materials Science and Engineering

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