The deposition of molecules featuring an extended conjugated system in thin films, self-assembled monolayers (SAMs) or as molecularly isolated species, on solid supports has emerged as a valuable tool to rationally engineer functional architectures with novel and unprecedented electronic properties.^1–8  Despite the wide variety of techniques available nowadays to deposit molecules on a surface^9–12  (vapor deposition, spin and drop-casting, Langmuir–Blodgett films, etc.), the investigation of the intra- and intermolecular interaction of molecules deposited on inorganic surfaces remains a very challenging task. In this context, the study of interactions between aromatic molecules in thin films and on surfaces covers a broad field of applications. Given the multitude of possible interactions and the broad range of associated energies, the underlying self-assembly processes are largely treated phenomenologically (e.g. 2-D spatial constraint and surface–molecule interactions).