Functionalized Supramolecular Nanoporous Arrays for Surface Templating

Abstract

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.