para‐Aminoazobenzenes – Bipolar Redox‐Active Molecules

Azobenzenes (ABs) are versatile compounds featured in numerous applications for energy storage systems, such as solar thermal storages or phase change materials. Additionally, the reversible one‐electron reduction of these diazenes to the nitrogen‐based anion radical has been used in battery applications. Although the oxidation of ABs is normally irreversible, 4,4’‐diamino substitution allows a reversible 2e– oxidation, which is attributed to the formation of a stable bis‐quinoidal structure. Herein, we present a system that shows a bipolar redox behaviour. In this way, ABs can serve not only as anolytes, but also as catholytes. The resulting redox potentials can be tailored by suitable amine‐ and ring‐substitution. For the first time, the solid‐state structure of the oxidized form could be characterized by X‐ray diffraction.