Microelectrode Arrays, Electrocatalysis, and the Need for Proper Characterization

Indirect electrochemical methods are a powerful tool for synthetic chemistry because they allow for the optimization of chemical selectivity in a reaction while maintaining the advantages of electrochemistry in terms of sustainability. Recently, we have found that such methods provide a handle for not only the synthesis of complex molecules, but also the construction of complex, addressable molecular surfaces. In this effort, the indirect electrochemical methods enable the placement or synthesis of molecules by any electrode or set of electrodes in a microelectrode array. The success of these surface-based reactions are typically evaluated with the use of fluorescence labelling studies. However, these fluorescence-based evaluations can be misleading. While they are excellent for determining that a reaction has occurred in a site-selective fashion on an array, they do not provide information on whether that reaction is the one desired or how well it worked. We describe here how the use of a “safety-catch” linker strategy allows for a more accurate assessment of reaction quality on an array, and then use that capability to illustrate how the use of transition metal mediated cross-coupling reactions on an array prevent unwanted background reactions that can occur on a polymer-coated electrode surface. The method enables a unique level of quality control for array-based transformations.