Highly Selective Intermolecular Cross-Coupling Reactions via a Persistent Radical Effect on Ag(111)
Achieving highly selective cross-coupling between two radicals remains a long-standing challenge due to competing homocoupling pathways. Here, we report a high-yield radical-based cross-coupling reaction on Ag(111), enabled by the persistent radical effect. Using bond-resolving scanning tunneling microscopy (BR-STM), we directly visualize reaction precursors, intermediates, and products at the single bond level. In our model system, we fulfill the stringent requirement of the persistent radical effect: coexisting high concentrations of persistent radicals with low concentrations of transient radicals. As a result, we achieve an unexpectedly high cross-coupling selectivity with yields exceeding 99%. Combining the experimental finding is combined with density functional theory (DFT) calculations, the reaction mechanism is clarified. Moreover, as radical cross-coupling is diffusion-controlled, we elucidate the kinetics of the persistent radical effect through systematic numerical modeling, Monte Carlo simulations, and control experiments on Cu(111).
Authors
- Jonas Björk (ORCID: https://orcid.org/0000-0002-1345-0006)
- Jinming Cai (ORCID: https://orcid.org/0000-0003-0869-1515)
- Jianchen Lu (ORCID: https://orcid.org/0000-0002-2120-4948)
- Zhai Yu-chun (ORCID: https://orcid.org/0000-0001-7602-2984)
- Lifeng Chi (ORCID: https://orcid.org/0000-0003-3835-2776)
- Haiping Lin (ORCID: https://orcid.org/0000-0002-9948-7060)
- Kaifeng Niu
- Johanna Rosén (ORCID: https://orcid.org/0000-0002-5173-6726)
- Qing Li (ORCID: https://orcid.org/0000-0002-6281-6342)
- Yong Zhang (ORCID: https://orcid.org/0000-0002-1303-0458)
- Yi Zhang (ORCID: https://orcid.org/0009-0001-4342-8088)
- Peipei Huang (ORCID: https://orcid.org/0009-0005-2362-7054)
- Huanjia Zhu
- Junbo Wang (ORCID: https://orcid.org/0009-0006-9955-7838)
Institutions
- Linköping University (SE)
- Kunming University of Science and Technology (CN)
- Soochow University (CN)
- Faculty (United Kingdom) (GB)
- Institute of Molecular Functional Materials (CN)
- Department of Physics, Mathematics and Informatics (BY)
- Division of Materials Science and Engineering (AU)
- Materials Design (France) (FR)
- Xi'an Jiaotong University (CN)
- Shaanxi Normal University (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-10-25
- DOI
- https://doi.org/10.1021/jacs.5c13021
- Primary Topic
- Surface Chemistry and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00