Skeletal Editing by Tip-Induced Chemistry

Skeletal editing of cyclic molecules has garnered considerable attention in the context of drug discovery and green chemistry with notable examples in solution-phase synthesis. Here, we extend the scope of skeletal editing to the single-molecule scale. We demonstrate tip-induced oxygen deletion and ring contraction of an oxygen-containing seven-membered ring on bilayer NaCl films to generate molecules containing the perylene skeleton. The products were identified and characterized at the atomic scale by atomic force microscopy and scanning tunneling microscopy. Insights into the reaction mechanisms were obtained by density functional theory calculations. Our work expands the toolbox of tip-induced chemistry for single-molecule synthesis.