Super‐Electron‐Donor Polymers: From Monomer Design to Redox Functionality

ABSTRACT The design flexibility of organic materials has enabled numerous applications for energy storage systems. However, few examples of low‐potential p‐type materials for the negative electrode are known in the field of organic batteries, particularly relevant for anion‐rocking‐chair full‐cells. Herein, we present a synthetic design to incorporate bridged 2,2′‐bipyridinium units, which in their reduced form are known as super‐electron‐donors, into a polymer structure. By adapting their synthesis, we obtain a hydroxy‐functionalized bridged bipyridinium salt with interesting structural features that are determined by molecular symmetry and environmental effects. Incorporation into a linear and cross‐linked poly(methacrylate) reduces its electrolyte solubility, enabling its initial electrochemical evaluation in lithium battery half‐cells. After testing electrodes with different compositions and screening electrolytes, we demonstrate that these polymers have the potential to function as electrode‐active materials, operating at an attractively low potential of 1.8 V vs. Li/Li + . This work highlights the opportunities of low‐potential 2,2′‐bipyridinium‐based polymers and demonstrates how synthetic design strategies can guide the development of novel organic electrode materials, providing a foundation for future research in this field.