Supramolecular nanopatterns of arylene–alkynylene squares with side chains of different lengths are investigated by scanning tunneling microscopy at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Self-sorting leads to the intermolecular interdigitation of alkoxy side chains of identical length. Voids inside and between the squares are occupied by intercalated solvent molecules, which numbers depend on the sizes and shapes of the nanopores. In addition, planar and non-planar coronoid polycyclic aromatic hydrocarbons (i.e., butyloxy-substituted kekulene and octulene derivatives) are found to be able to intercalate into the intramolecular nanopores.

A series of benzoic and terephthalic acid derivatives and their corresponding ethyl esters have been synthesized. These are decorated with dendritic units carrying alkoxy chains that differ in the number of alkoxy groups and/or their substitution pattern. These molecules were deposited from solution on highly oriented pyrolytic graphite, and the resulting supramolecular surface patterns have been studied by scanning tunneling microscopy at the solid/liquid interface. Thus, we were able to perform a systematic study on the influence of orthogonal functional groups governing the supramolecular assembly, that is, the alkoxy chains of dendritic units and the carboxylic acid (ester) functions, on the intermolecular interactions, that is, van der Waals interactions and hydrogen bonding between the adsorbed species that drive the pattern formation.