Adatom Coadsorption with Three-Dimensional Cyclophanes on Ag(111)

The structure of molecular adlayers is of great interest for surface functionalization. As molecular complexity increases, the subtle interplay of the relevant interactions becomes more difficult to unravel. Here, we present a scanning tunneling microscope (STM) and atomic force microscope study along with free-energy calculations using density functional theory on two closely related NDI-cyclophane molecules. These three-dimensional double-decker molecules are designed to attach to the substrate with one subunit while the other functional moiety is exposed to the environment. The molecular arrangements obtained on Ag(111) are rationalized by the inclusion of adatoms from the substrate into the structure. The presence of adatoms is identified by a drastic change in corrugation of the STM images that takes place at moderate bias voltages. Our calculations using density functional theory of the system’s free-energy yield that two adatoms favorably coadsorb with the molecules.