Surface patterning using scanning electrochemical microscopy to locally trigger a “click” chemistry reaction

• Electroassisted interfacial click chemistry at a SECM tip
• Ferrocene redox mediator linked to 4-azido diazonium layer within a micrometric localized zone
• The clicked ferrocene mediated redox activity of ferrocyanide allowed imaging the ultrathin layered spot.

We report on the surface micropatterning of conductive surfaces via the electrochemical triggering of a click reaction, the copper(I) catalyzed azide–alkyne cycloaddition reaction (CuAAC) by SECM via a two-step approach: (i) functionalization on the entire surface with azido-aryl groups by using the diazonium approach followed by (ii) the covalent linkage of alkyne-bearing ferrocene by CuAAC within a local area by SECM. More precisely, the click reaction was triggered by Cu(I) catalyst generation for 30 min at the SECM tip positioned ≈ 10 μm above the azido-aryl modified surface. The dimension of the spot obtained under these conditions was ≈ 75 μm. The electrochemical imaging by SECM of the ultra thin area locally clicked with ferrocene moieties was made thanks to the electrocatalytic properties of the ferrocene modified surface towards ferrocyanide electrooxidation. This local clicking procedure opens the gate to further controlled functionalization of restricted small substrates.