The Influence of Molecular Configurations on the Desulfonylation Reactions on Metal Surfaces
Junbo Wang1,2,#, Kaifeng Niu1,3,#, Chaojie Xu1, Huaming Zhu2, Honghe Ding4, Dong Han4, Yuanjing Zheng1,Jiahao Xi1, Sifan You1, Chuan Deng2, Haiping Lin2, Johanna Rosen3, Junfa Zhu4,*,Jonas Björk3,*, Qing Li2,*, and Lifeng Chi1,5,*,
1Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, China
2School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710119, China
3Department of Physics, Chemistry and Biology, IFM, Linköping University, Linköping 58183, Sweden
4National Synchrotron Radiation Laboratory,Department of Chemical Physics and Key Laboratory ofSurface and Interface Chemistry and Energy Catalysis ofAnhui Higher Education Institutes,University of Science and Technology ofChina, Hefei 230029, China
5Department of Materials Science and Engineering, Macau University of Science and Technology, Macau 999078, China
On-surface synthesis is a powerful methodology for the fabrication of low-dimensional functional materials. The precursor molecules usually anchor on different metal surfaces via similar configurations. The activation energies are therefore solely determined by the chemical activity of the respective metal surfaces. Here, we studied the influence of the detailed adsorption configuration on the activation energy on different metal surfaces. We systematically studied the desulfonylation homocoupling for a molecular precursor on Au(111) and Ag(111) and found that the activation energy is lower on inert Au(111) than on Ag(111). Combining scanning tunneling microscopy observations, synchrotron radiation photoemission spectroscopy measurements, and density functional theory calculations, we elucidate that the phenomenon arises from different molecule–substrate interactions. The molecular precursors anchor on Au(111) via Au–S interactions, which lead to weakening of the phenyl–S bonds. On the other hand, the molecular precursors anchor on Ag(111) via Ag–O interactions, resulting in the lifting of the S atoms. As a consequence, the activation barrier of the desulfonylation reactions is higher on Ag(111), although silver is generally more chemically active than gold. Our study not only reports a new type of on-surface chemical reaction but also clarifies the influence of detailed adsorption configurations on specific on-surface chemical reactions.