Controlling\nthe Selectivity of Reaction Products by\nTransmetalation on a Ag(111) Substrate

On-surface\nsynthesis has shown great promise in the precise bottom-up\npreparation of molecular nanostructures. Apart from the direct C–C\ncoupling reaction pathway, an alternative strategy is to exploit the\nmetal–organic interactions provided by integrated metals for\npreassembly, which exhibit high reversibility and can anchor specific\nconformations of molecular precursors, thus allowing the precise construction\nof nanostructures with improved reaction selectivity. Previous studies\nhave mainly been devoted to the construction of target reaction products\nthrough the incorporation of metal atoms, ranging from intrinsic to\nextrinsic atoms on metal substrates and, more recently, to their cooperative\neffects. However, the formation of different covalent nanostructures\nby competitive interactions between intrinsic and extrinsic adatoms\nremains elusive. Herein, we controlled the selectivity of covalent\nreaction products from isomerically specific <i>trans</i>-chains to <i>cis</i>-rings, resulting from the transmetalation\nof intrinsic Ag adatoms to extrinsic Na atoms on a Ag(111) substrate.\nOur results exhibit the competitive interactions between intrinsic\nand extrinsic metal atoms in real space and demonstrate their influence\non the selectivity of reaction products, which should broaden the\nregulatory strategies for on-surface synthesis that shed light on\nthe controllable and selective synthesis of target covalent nanostructures.