Locally induced and self-induced "electroclick" onto a self-assembled monolayer: writing and reading with SECM under...

Localized "electroclick" was achieved on azido-terminated self-assembled monolayers using Scanning Electrochemical Microscopy (SECM) in feedback mode, in which the substrate is not electrically connected (unbiased conditions). The method allows both the local immobilization of diverse functional moieties and the monitoring of each modification step at a micrometer scale. Conditions of the "click" coupling reaction were optimized especially to avoid the deposit of metallic copper by the choice of a specific ligand to stabilize the Cu(I) species. The catalytic efficiency in localized "electroclick" reaction of Cu(II)TMPA (TMPA: tris(2-pyridylmethyl)amine) as the "click" catalyst was compared with a derivative containing an alkyne group Cu(II)6eTMPA, the same molecule playing the role of the catalyst and the substrate. Evidences for surface self-catalysis propagation are demonstrated through SECM imaging showing a random 2D progression of the catalytic modification.