Functionalized Supramolecular Nanoporous Arrays for Surface Templating

Controlled self‐assembly and chemical tailoring of bimolecular networks on surfaces is demonstrated using structural derivatives of 3,4:9,10‐perylenetetracarboxylic diimide (PTCDI) combined with melamine (1,3,5‐triazine‐2,4,6‐triamine). Two functionalised PTCDI derivatives have been synthesised, Br2–PTCDI and di(propylthio)–PTCDI, through attachment of chemical side groups to the perylene core. Self‐assembled structures formed by these molecules on a Ag–Si(111)${\sqrt{3}}$×${\sqrt{3}}$R30° surface were studied with a room‐temperature scanning tunneling microscope under ultrahigh vacuum conditions. It is shown that the introduction of side groups can have a significant effect upon both the structures formed, notably in the case of di(propylthio)–PTCDI which forms a previously unreported unimolecular hexagonal arrangement, and their entrapment behaviour. These results demonstrate a new route of functionalisation for network pores, opening up the possibility of designing nanostructured surface structures with chemical selectivity and applications in nanostructure templating. Keeping functional groups at bay: The introduction of functional groups to the “bay” region of perylene tetracarboxylic diimides significantly influences surface‐based self‐assembly processes leading to either unimolecular or bimolecular hexagonal surface networks, exploiting either homo‐ or hetero‐molecular hydrogen bonding.