The surface-assisted reaction is a key process for graphene nanoribbons (GNRs) synthesis. So far, anthracene based compounds, as represented by 10,10’-dibromo-9,9’-bianthracene, are most-used molecular precursors for GNRs synthesis. However, even the simple anthracene based precursor molecules exhibit a variety of reactivity because the on-surface synthesis includes hierarchical reactions such as dehalogenation, polymerization, and cyclodehydrogenation. Considering that the reactivity of the small precursor molecules determines the final structure of GNRs, the key to success for synthesizing tailored GNRs is the deep understanding the relationship between the reactivity of the molecules and the geometry on the catalytic metal surface.

Here, we investigated the reactivity of a fluorinated precursor molecule during the GNR formation. The fluorine atoms were introduced at 2,3,6,7-positions of an anthracene sandwiched by 9-bromoanthracenes in order that the effect of fluorine substitution at the edge positions of polyanthrylene and GNRs would be investigated. Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) indicate the formation of the edge-fluorinated polyanthrylenes. Interestingly, the following cyclodehydrogenation yields GNRs, dissociating the carbon-fluorine bonds at the edge positions of polyanthrylenes. Namely, the strong C-F bond survived during the polymerization step, but the following cyclodehydrogenation cleaved the C-F bond. Theoretical calculation implies that the structure of the intermediate state during the cyclodehydrogenation played an important role in the fluorine dissociation. Thus, the lessons from the dissociation of the strong C-F bond, which is believed as one of the strongest bonding in the solution chemistry, would provide the synthetic access to the proper design of precursor molecules for edge-functionalized GNRs.