Au adatoms in self-assembly of benzenethiol on the Au(111) surface.

Self-assembly of benzenethiol at low coverage on Au(111) was studied using low-temperature scanning tunneling microscopy. Phenylthiolate species (PhS), formed by thermal dehydrogenation of the parent PhSH molecule, was found to self-assemble into surface-bonded complexes with gold adatoms. Each complex involves two PhS species and one gold adatom. The PhS species form either cis- or trans-geometry relative to each other. At a higher coverage, the complexes coalesce, most likely due to the formation of weak C-H...S hydrogen bonds facilitated by the spatial arrangement of the PhS groups. Our findings thus establish that the self-assembly of arenethiols on the Au(111) surface is driven by gold adatom chemistry, which has recently been found to be the key ingredient in the self-assembly of alkanethiols on gold.