Balancing Intermolecular and Molecule–Substrate Interactions in Supramolecular Assemblies

Abstract Self‐assembly of functional supra‐molecular nanostructures is among the most promising strategies for further development of organic electronics. However, a poor control of the interactions driving the assembling phenomena still hampers the tailored growth of designed structures. Here exploration of how non‐covalent molecule‐substrate interactions can be modified on a molecular level is described. For that, mixtures of DIP and F16CuPc, two molecules with donor and acceptor character, respectively are investigated. A detailed study of their structural and electronic properties is performed. In reference to the associated single‐component layers, the growth of binary layers results in films with strongly enhanced intermolecular interactions and consequently reduced molecule‐substrate interactions. This new insight into the interplay among the aforementioned interactions provides a novel strategy to balance the critical interactions in the assembly processes by the appropriate choice of molecular species in binary supra‐molecular assemblies, and thereby control the self‐assembly of functional organic nanostructures.