Unusual Scaffold Rearrangement in Polyaromatic Hydrocarbons Driven by Concerted Action of Single Gold Atoms on a Gold Surface

• Published in: Angewandte Chemie 2022-12, Vol.134 (50), p.n/a
• Main Authors: Mendieta‐Moreno, Jesús I., Mallada, Benjamin, Torre, Bruno, Cadart, Timothée, Kotora, Martin, Jelínek, Pavel
• Format: Article
• Language: English
• Subjects: (PAH) Polyaromatic Hydrocarbon; (SPM) Scanning Probe Microscopy; Adatoms; Catalysis; Catalytic activity; Chemical synthesis; Chemistry; Cleavage; Gold; Hydrocarbons; on-Surface Synthesis; Polycyclic aromatic hydrocarbons; Scaffolds
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202208010

Chemical transformation of polyaromatic hydrocarbon (PAH) molecules following different reaction strategies has always been the focus of organic synthesis. In this work, we report the synthesis of a PAH molecule, formation of which consists of an unusual C−C bond cleavage accompanied by a complex π‐conjugated molecular scaffold rearrangement. We demonstrate that the complex chemical transformation is steered by concerted motion of individual Au0 gold atoms on a supporting Au(111) surface. This observation underpins the importance of single‐atom catalysis mediated by adatoms in on‐surface synthesis as well as catalytic activity of single Au0 atoms facilitating cleavage of covalent carbon bonds. The on‐surface synthesis of a polyaromatic hydrocarbon molecule is described. Mechanistically, the synthesis involves an unusual C−C bond cleavage catalyzed by Au adatoms with a molecular scaffold rearrangement. This rearrangement in the π‐conjugated molecular scaffold is possible because of the concerted action of two Au adatoms that catalyze the reaction on the gold surface.