Activating Redox Chemistry of Benzene Rings in π‐d Conjugated Coordination Polymers Toward High‐Performance Zinc‐Ion Batteries

Abstract π‐d Conjugated coordination polymers (CCPs) have attracted much attention as electrode materials of batteries owing to their high conductivity, diverse structure, and tunability. However, the low energy density of CCP electrodes caused by insufficient active sites limits their practical application. Herein, a molecular engineering strategy is proposed to activate the electrochemical activity of inert benzene rings by regulating their π‐electron property with precise modulation of their π‐electron configuration. As proof of concept, a novel CCP (TAPZ‐Ni) is designed and synthesized based on an electroactive organic ligand (TAPZ) with an extended π‐conjugated system. The enhanced π‐d conjugation in TAPZ‐Ni induces remarkable electron delocalization across the coordination framework, significantly elevating the π‐electron density of benzene rings and thereby unlocking their previously inaccessible Zn 2 ⁺ storage capability. As a result, the TAPZ‐Ni CCP cathode for zinc‐ion batteries displays a high discharge capacity (300.1 mAh g −1 at 0.1 A g −1 ), satisfactory lifespan (stability cycles over 500 times at 0.2 A g −1 ), and good anti‐freezing performances (172.9 mAh g −1 at −40 °C). This work establishes a fundamental design principle for activating the electrochemical potential of CCP materials through π‐electron manipulation, providing a universal platform for developing high‐performance energy storage systems.