Supramolecular Nanopatterns of Molecular Spoked Wheels with Orthogonal Pillars: The Observation of a Fullerene Haze

Molecular spoked wheels with intraannular functionalizable pillars are synthesized in a modular approach. The functionalities at their ends are variable, and a propargyl alcohol, a [6,6]‐phenyl‐C61‐butyrate, and a perylene monoimide are investigated. All compounds form two‐dimensional crystals on highly oriented pyrolytic graphite at the solid–liquid interface. As determined by submolecularly resolved scanning tunneling microscopy, the pillars adopt equilibrium distances of 6.0 nm. The fullerene has a residual mobility, limited by the length of the flexible connector unit. The experimental results are supported and rationalized by molecular dynamics simulations. These also show that, in contrast, the more rigidly attached perylene monoimide units remain oriented along the surface normal and maintain a smallest distance of 2 nm above the graphite substrate. The robust packing concept also holds for cocrystals with molecular hexagons that expand the pillar–pillar distances by 15 % and block unspecific intercalation. A modular synthetic approach paves the way to nanoscale platform molecules for supramolecular graphite surface patterns at the solid–liquid interface. While a perylene dye bound at the end of the pillar remains fixed above the molecule center and points into solution, a fullerene ester bound at the same position performs a tumbling motion that translates as a “haze” in the otherwise submolecularly resolved images.