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Adsorption and self-organization of organic molecules on solid substrates have been studied extensively in vacuum and at solid-liquid interfaces. Under electrochemical conditions, however, an often exceptional level of control over adsorption and self-organization can be achieved. The source of this control lies in modulating the strength of the interactions between adsorbates, substrate, and electrolyte through the electric field at the electrode-electrolyte interface and has both thermodynamic and kinetic origins and implications. This article briefly introduces the most important substrates for studying adsorption and self-organization under electrochemical control and the main techniques used. We then discuss the principles responsible for switching and tuning supramolecular structures under electrochemical control, by analyzing representative examples.
Corresponding author: Stijn F. L. Mertens (mertens).