Octaphyrin(1.0.1.0.1.0.1.0) as an Organic Electrode for Li and Na Rechargeable Batteries

Organic electrode materials for rechargeable batteries have come into the spotlight due to their structural tunability and diversity. In this study, it is found that bisnickel(II) meso‐mesityloctaphyrin(1.0.1.0.1.0.1.0) (Oct) is exhibiting multiple oxidation states with extended π‐conjugation pathways to afford an active electrode material in Li and Na‐organic batteries and secure interactions with Li+ (or Na+) and anions enabling efficient dual ionic charge/discharge behaviors. Cyclic voltammograms of the Oct electrode elucidate constantly reversible redox processes in both Li and Na organic batteries and pseudocapacitive behaviors at high currents. Subsequent absorption transformations in CV‐UV/VIS/NIR spectroscopic analysis and TD‐DFT calculations upon the different redox states of Oct conclusively indicate that six electrons are involved in redox‐interconversions per unit cycle with corresponding absorption transformations, which also assessed with charge‐and‐discharge cell capacities. Significant contributions of the pseudocapacitive processes over the diffusion‐controlled processes proceeding in Li‐ and Na‐Oct cells induced fast charge/discharge performance and long‐term cyclability. It is the first report to deliver sustainable expanded porphyrinoid organic electrode material for lithium and sodium organic batteries with the comprised mechanisms.