On-Surface Hydrogen-Induced Covalent Coupling of Polycyclic Aromatic Hydrocarbons via a Superhydrogenated Intermediate

Abstract: The activation and subsequent covalent coupling of polycyclic aromatic hydrocarbons (PAHs) are of great interest in fields like chemistry, energy, biology, or health, among others. However, this is not a trivial process. So far, it is based on the use of catalysts that drive and increase the efficiency of the reaction. Here, we report on an unprecedented method in which the dehydrogenation and covalent coupling is thermally activated in the presence of atomic hydrogen and a surface. This mechanism, which requires of the superhydrogenation of the PAHs, has been characterized by high-resolution scanning tunnelling microscopy (STM) and rationalized by density functional theory (DFT) calculations. This work opens a door toward the formation of covalent, PAH-based, macromolecular nanostructures on low-reactive surfaces, thus facilitating its applicability.