On-Surface Synthesis within a Porphyrin Nanoring Template.

On-surface synthesis provides a route for the production of 1D and 2D covalently bonded polymeric structures. Such reactions are confined to the surface of a substrate and the catalytic properties of the substrate are often utilised to initiate the reaction. Recent studies have focused on the properties of various crystallographic planes of metallic substrates, as well as native surface features such as step-edges, in an effort to provide control over the pathway of the reaction and the resultant products. An alternative approach is to template the catalytic surface with a porous molecular overlayer; giving rise to well-defined surface regions within which an on-surface reaction may be confined. Here we present a methodology where macromolecular templates are used to confine an on-surface reaction. Cyclic porphyrin polymers, nanorings - consisting of 40 porphyrin units with internal diameter 13 nm, are used to form a template on a Au(111) surface, and an on-surface Ullmann-type coupling reaction is initiated within the nanoring template. The surface confined template and covalently coupled reaction products are investigated and characterised with scanning tunnelling microscopy.