On-surface synthesis has shown great promise in the precise bottom-up preparation of molecular nanostructures. Apart from the direct C–C coupling reaction pathway, an alternative strategy is to exploit the metal–organic interactions provided by integrated metals for preassembly, which exhibit high reversibility and can anchor specific conformations of molecular precursors, thus allowing the precise construction of nanostructures with improved reaction selectivity. Previous studies have mainly been devoted to the construction of target reaction products through the incorporation of metal atoms, ranging from intrinsic to extrinsic atoms on metal substrates and, more recently, to their cooperative effects. However, the formation of different covalent nanostructures by competitive interactions between intrinsic and extrinsic adatoms remains elusive. Herein, we controlled the selectivity of covalent reaction products from isomerically specific trans-chains to cis-rings, resulting from the transmetalation of intrinsic Ag adatoms to extrinsic Na atoms on a Ag(111) substrate. Our results exhibit the competitive interactions between intrinsic and extrinsic metal atoms in real space and demonstrate their influence on the selectivity of reaction products, which should broaden the regulatory strategies for on-surface synthesis that shed light on the controllable and selective synthesis of target covalent nanostructures.

中文翻译：

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通过在 Ag（111） 衬底上进行金属转移来控制反应产物的选择性


表面合成在分子纳米结构的精确自下而上制备中显示出巨大的前景。除了直接的 C-C 偶联反应途径外，另一种策略是利用集成金属提供的金属-有机相互作用进行预组装，它表现出高可逆性，并且可以锚定分子前体的特异性构象，从而允许精确构建具有更高反应选择性的纳米结构。以前的研究主要致力于通过掺入金属原子构建目标反应产物，范围从金属衬底上的本征原子到外征原子，以及最近的协同效应。然而，通过本征和外征 adatom 之间的竞争性相互作用形成不同的共价纳米结构仍然难以捉摸。在此，我们控制了共价反应产物从异构体特异性反式链到顺环的选择性，这是由于 Ag（111） 衬底上的本征 Ag 原子向外源性 Na 原子的金属化而产生的。我们的结果展示了真实空间中本征和外源性金属原子之间的竞争性相互作用，并证明了它们对反应产物选择性的影响，这应该拓宽表面合成的调节策略，从而阐明目标共价纳米结构的可控和选择性合成。