J. Phys. Chem. C, 129, 6283−6291 (2025)
Site Selectivity of the σ‑Bond Metathesis on a Persilylated Decaethynyldiphenyl
Hua Yang1, Philipp Alexander Held2, Dirk Leifert2, Harald Fuchs3,*, Armido Studer2,*, Zhixin Hu4,* and Hong-Ying Gao1,*
1 Collaborative Innovation Center of Chemical Science and Engineering, Key Laboratory for Green Chemical Technology of Ministry of Education and School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P. R. China.
2 Organisch-Chemisches Institut, University of Münster, Münster 48149, Germany.
3 Center for Nanotechnology, University of Münster, Münster 48149, Germany.
4 Center for Joint Quantum Studies and Department of Physics, School of Science, Tianjin University, Tianjin 300350, P. R. China.
* uchsh@unimuenster.de, studer@uni-muenster.de, zhixin.hu@tju.edu.cn, gaohongying@tju.edu.cn
Abstract
The selective functionalization of organic molecules is a cornerstone in chemistry, enabling the design and assembly of tailored molecular architectures. The controlled, site-selective functionalization of the same chemical groups within one molecule is challenging and hinders the synthesis of specific organic nanostructures, especially in on-surface chemistry. Here, using low-temperature scanning tunneling microscopy and density functional theory calculation, the site-selective desilylation at para, meta, and ortho positions of persilylated decaethynyldiphenyl in the σ-bond metathesis reaction with 2,6-naphthalenedicarboxylic acid on the Ag(111) surface is reported. The site selectivity observed stems from the varying bulky silyl configurations at different molecular positions, leading to distinct reaction barriers in the σ-bond metathesis. These findings provide insight into the on-surface siteselective activation of large aromatic compounds.
