Unveiling Intermolecular Frustrated Lewis Pairs in Single‐Molecule Junctions
Intermolecular frustrated Lewis pairs (FLPs) play vital roles in catalysis yet remain undetectable at the single-molecule scale due to their ultralow interaction energies and transient nature. This limitation obstructs mechanistic understanding of weak orbital coupling in molecular systems. To address this, we engineered a sterically hindered molecular probe (OPE-Py-M) that forms stable in situ FLP adducts with B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> (BCF) within single-molecule junctions. Using scanning tunneling microscopy break junction (STM-BJ) techniques, we observed a quantifiable conductance attenuation from 10<sup>-4.39</sup> to 10<sup>-4.78</sup> G<sub>0</sub> upon FLP formation, a signature validated by NMR upfield shifts and UV-Vis charge-transfer bands. This work establishes single-molecule conductance as an ultrasensitive probe for orbital perturbations below hydrogen-bond energy thresholds, enabling unprecedented investigation of noncovalent interactions in molecular electronics and self-assembly.
Authors
- Xunshan Liu (ORCID: https://orcid.org/0000-0003-1537-258X)
- Yun Xing (ORCID: https://orcid.org/0000-0003-2552-8162)
- Hu Zhang (ORCID: https://orcid.org/0000-0001-8726-8605)
- Wei Liu (ORCID: https://orcid.org/0000-0002-6665-220X)
- Jun Hu (ORCID: https://orcid.org/0000-0002-7575-2165)
- Haoran Sun (ORCID: https://orcid.org/0000-0001-7299-6415)
Institutions
- Zhejiang Sci-Tech University (CN)
- Chinese Academy of Sciences (CN)
- Changchun Institute of Applied Chemistry (CN)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-10-27
- DOI
- https://doi.org/10.1002/chem.202502694
- Primary Topic
- Molecular Junctions and Nanostructures
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Natural Science Foundation of Jilin Province
- National Natural Science Foundation of China
- People's Government of Jilin Province
- Zhejiang Sci-Tech University