Schatz Dominic, Baumert Marcel E, Kersten Marie C, Schneider Finn M, Nielsen Mogens Brøndsted, Hansmann Max M, Wegner Hermann A
Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392, Gießen, Germany.
Center of Materials Research (ZfM/LaMa), Justus Liebig University, Heinrich-Buff-Ring 16, 35392, Gießen, Germany.
Angew Chem Int Ed Engl. 2024 Sep 2;63(36):e202405618. doi: 10.1002/anie.202405618. Epub 2024 Jul 29.
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 radical anion 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.
偶氮苯（ABs）是一种用途广泛的化合物，在储能系统的众多应用中都有其身影，比如太阳能热储存或相变材料。此外，这些重氮化合物可逆的单电子还原为氮基自由基阴离子已被用于电池应用中。尽管ABs的氧化通常是不可逆的，但4,4'-二氨基取代允许进行可逆的2e氧化，这归因于形成了稳定的双醌型结构。在此，我们展示了一个呈现双极氧化还原行为的体系。通过这种方式，ABs不仅可以用作阳极电解液，还可以用作阴极电解液。由此产生的氧化还原电位可以通过合适的胺基和环取代来进行调整。首次通过X射线衍射对氧化态的固态结构进行了表征。
