Single‐Molecule Solvolysis Reaction Dynamics under Electrostatic Catalysis and Proton Tunneling
A central goal of chemical mechanism research is to provide a comprehensive interpretation of chemical reaction pathways to clarify the evolution patterns of reactions. In this work, we present an unprecedented comprehensive monitoring of the elementary reaction pathways of the S<sub>N</sub>1 solvolysis on an in situ real-time single-molecule electrical detection platform. Through precise control of oriented external electric fields, we capture two short-lived protonated intermediates at the single-molecule level and elucidate their roles in the reaction. Both temperature- and isotope-dependent experiments, in combination with theoretical simulations, reveal crucial roles for the hydrogen-bonded acetic-acid-mediated triple-proton-transfer and the proton tunneling effect in the interconversion of these two intermediates. This work highlights the precise manipulation of chemical reactions by electrostatic fields and opens up a universal route to discover unknown intermediates or novel phenomena in the processes of material transformation and life activities.
Authors
- Bao‐Liang Zhong (ORCID: https://orcid.org/0000-0002-7229-1519)
- Ganglong Cui (ORCID: https://orcid.org/0000-0002-9752-1659)
- Jie Hao (ORCID: https://orcid.org/0000-0003-1276-2363)
- Haobin Wang (ORCID: https://orcid.org/0000-0002-3532-7770)
- Wei‐Hai Fang (ORCID: https://orcid.org/0000-0002-1668-465X)
- Xuefeng Guo (ORCID: https://orcid.org/0000-0001-5723-8528)
- Wei Huang (ORCID: https://orcid.org/0000-0001-7004-6408)
- Chen Yang (ORCID: https://orcid.org/0000-0002-4521-0816)
- Yong Yan (ORCID: https://orcid.org/0000-0001-6200-5948)
- Linghai Xie (ORCID: https://orcid.org/0000-0001-6294-5833)
- Jiajia Yang (ORCID: https://orcid.org/0000-0002-6972-8708)
- Yilin Guo (ORCID: https://orcid.org/0009-0007-8410-2328)
- Xinmiao Xie
Institutions
- King University (US)
- Peking University (CN)
- Nankai University (CN)
- Beijing Normal University (CN)
- Nanjing University of Posts and Telecommunications (CN)
- Beijing National Laboratory for Molecular Sciences (CN)
- Sichuan Normal University (CN)
- University of Colorado Denver (US)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-03-04
- DOI
- https://doi.org/10.1002/anie.202425097
- Citations
- 2
- Primary Topic
- Molecular Junctions and Nanostructures
- Type
- article
- Field-Weighted Citation Impact
- 1.46