Functionalized Supramolecular NanoporousArraysfor Surface Templating

Controlled self-assembly and chemical tailoring of bimolecular net- works 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- ADI, through attach- ment of chemical side groups to the perylene core. Self-assembled struc- tures formed by these molecules on a Ag-SiA ffiffiffi 3 p 8 ffiffiffi 3 p R308 surface were studied with a room-temperature scan- ning tunneling microscope under ultra- high 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 en- trapment behaviour. These results demonstrate a new route of functional- isation for network pores, opening up the possibility of designing nanostruc- tured surface structures with chemical selectivity and applications in nano- structure templating.