Controlling molecular deposition and layer structure with supramolecular surface assemblies

Selective non-covalent interactions have been widely exploited in solution-based chemistry to direct the assembly of molecules into nanometre-sized functional structures such as capsules, switches and prototype machines1,2,3,4,5. More recently, the concepts of supramolecular organization have also been applied to two-dimensional assemblies on surfaces6,7 stabilized by hydrogen bonding8,9,10,11,12,13,14, dipolar coupling15,16,17 or metal co-ordination18. Structures realized to date include isolated rows8,13,14,15, clusters9,10,18 and extended networks10,11,12,17, as well as more complex multi-component arrangements16. Another approach to controlling surface structures uses adsorbed molecular monolayers to create preferential binding sites that accommodate individual target molecules19,20. Here we combine these approaches, by using hydrogen bonding to guide the assembly of two types of molecules into a two-dimensional open honeycomb network that then controls and templates new surface phases formed by subsequently deposited fullerene molecules. We find that the open network acts as a two-dimensional array of large pores of sufficient capacity to accommodate several large guest molecules, with the network itself also serving as a template for the formation of a fullerene layer.