On-Surface Hydrogen/Deuterium Isotope Exchange in Polycyclic Aromatic Hydrocarbons

Hydrogen plays important roles in the on-surface synthesis of carbon-based materials in ultra-high vacuum. The complex interplay between hydrogen and surface-adsorbed polycyclic aromatic hydrocarbons (PAHs) is tracked by in situ time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with isotope labeling. In situ deuterium labeling of prototypical PAHs, coronene (CR) and 7-armchair graphene nanoribbons (GNRs), on Au(111) is achieved by annealing either in D₂ gas or in the vapor of perdeuterio-acenaphthene. By following the mass spectra of in situ deuterated CR mixed with hydrogen-CR, it is demonstrated that PAHs adsorbed at hot Au(111) surfaces continuously exchange hydrogen atoms. Also, D₂ present during the Ullmann coupling step leads to incorporation of deuterium and to shorter GNRs.