Supramolecular Electropolymerization

Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self‐assembly and self‐organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation‐growth of triarylamine monomers can be triggered by electrochemistry in various solvents. The involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode. To illustrate the potential of this methodology, supramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to a single DC electric field, reaching a precision unprecedented in the literature. Trigger happy: The direct electrochemical oxidation of triarylamines at anodes triggers their nucleation and growth into supramolecular polymers. This mechanism can be defined as a supramolecular electropolymerization process. It is used to grow and precisely address single nanowires over a distance of 50 μm between two electrodes in a direct current electric field.