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 onsurface chemical reactions.

Two-dimensional (2D) tessellation of organic species acquired increased interests recently because of their potential applications in physics, biology, and chemistry. 2D tessellations have been successfully constructed on surfaces via various intermolecular interactions. However, the transformation between 2D tessellation lattices has been rarely reported. Herein, we successfully fabricated two types of Kagome lattices on Cu(111). The former phase exhibits (3,6,3,6) Kagome lattices, which are stabilized via the intermolecular hydrogen bond interactions. The latter phase is formed through direct chemical transferring from the former one maintaining almost the same Kagome lattices, except for that the unit cell rotates for 4°. Detailed scanning tunneling microscopy and density functional calculation studies reveal that the chemical transformation is achieved by the formation of the N−Cu−N metal−organic bonds via dehydrogenation reactions of the amines.

On-surface synthesis of phenylenes is a promising strategy to form extended πconjugated frameworks but normally lacks selectivity in achieving uniform products. Herein we demonstrate that the debromination reaction of 2,3-dibromophenazine (DBPZ) on Au(111) and Ag(111) surfaces can vary significantly considering the involvement of metal−organic hybrids (MOHs). On Au(111), [2 + 2] and [2 + 2 + 2] cycloadditions facilitate instantaneously upon the debromination occurring, while on Ag(111), several MOHs have been observed under sequential thermal annealing, leading to finally the uniform [2 + 2] cycloaddition product exclusively. By means of scanning tunneling microscopy (STM) and bond-resolved atomic force microscopy (BR-AFM), we have unambiguously depicted the chemical structure of related reaction intermediates and unraveled the undocumented role of hierarchical evolution of MOHs in steering the chemical selectivity.