Highly Selective On-Surface [2 + 2] Cycloaddition Induced by Hierarchical Metal-Organic Hybrids.

On-surface synthesis of phenylenes is a promising strategy to form extended π-conjugated 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.