Hierarchical Dehydrogenation Reactions on a Copper Surface

Hierarchical control of chemical reactions is being considered as one of the most ambitious and challenging topics in modern organic chemistry. In this study, we have realized the one-by-one scission of the X–H bonds (X = N and C) of aromatic amines in a controlled fashion on the Cu(111) surface. Each dehydrogenation reaction leads to certain metal–organic supramolecular structures, which were monitored in single-bond resolution via scanning tunneling microscopy and noncontact atomic force microscopy. Moreover, the reaction pathways were elucidated from X-ray photoelectron spectroscopy measurements and density functional theory calculations. Our insights pave the way for connecting molecules into complex structures in a more reliable and predictable manner, utilizing carefully tuned stepwise on-surface synthesis protocols.