Visualizing the Hierarchical Evolution of Aryl–Metal Bonding in Organometallic Nanostructures on Ag(111)

• Published in: The journal of physical chemistry letters 2023-12, Vol.14 (48), p.10819-10824
• Main Authors: Gao, Yuhong, Zhang, Zhaoyu, Yi, Zewei, Zhang, Chi, Xu, Wei
• Format: Article
• Language: English
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.3c02950

On-surface dehalogenative coupling reactions are promising for constructing nanostructures with diverse properties and functionalities. Extensive efforts have been devoted to single aryl-halogen (C-X) substituents and substitutions at various functionalization sites (typically including meta- and para-substitutions) to generate aryl-aryl single bonds. Moreover, multiple C-X substituents at the ortho-site and the peri- and bay-regions have been applied to create a variety of ring scaffolds. However, for multiple C-X substituents, the hierarchy of aryl-metal bond formation and dissociation remains elusive. Herein, by combining scanning tunneling microscopy imaging and density functional theory calculations, we have visualized and demonstrated the hierarchical evolution of aryl-metal bonding in organometallic intermediates involved in a dehalogenative coupling reaction on Ag(111), using a molecular precursor with both para-substitution and potential bay-region substitution. Our results elucidate how metal atoms are progressively embedded into and removed from organometallic intermediates, enhancing the understanding of on-surface dehalogenative coupling reactions for the controlled construction of the desired nanostructures.