Donor‐Π‐Acceptor Self‐adaptive Conjugated Perylene Derivative with Low Solubility, High Capacity, and Swift Ion Transport Kinetics for High performance Organic Cathode

Organic perylene has been heralded as a promising candidate due to abundant structural diversity and tunability. However, its practical application is severely plagued by facile solubility, scarce redox‐active sites, and andante kinetics behaviors. Herein, the perylene derivative (DPL), i.e. (1,6,7,12‐tetrakis (4‐tert‐butylphenoxy) perylene‐3,4,9,10‐tetracarboxylic dianhydride) conjugates with polyoxime ester (PO), and is further nested with N, P grafted hollow matrix with anchored Cu single atoms (Cu‐NPC). Such Cu‐NPC@DPL@PO with helically twisted donor‐π‐acceptor (D‐π‐A) conjugate bridged by Cu atoms was evaluated for K+ storage. Based on extended π‐π conjugated structure, intensified interactions between PO and DPL, the minimal solubility of DPL is approached. Together with the core‐shell solvation structure and compact cathode electrolyte interface (CEI) synergistically improves its long lifespan. The abundant stabled radical nitroxides, isocyano groups, and sp‐C sites, contribute greatly to the capacity elevation. The twisted D‐π‐A self‐adaptive coordination conjugate (TSCC) significantly elevates the distortion towards for the easier tendency to flipping and vibrating and thus expedited kinetics behaviors. Consequently, Cu‐NPC@DPL@PO reconciles the trade‐off between fast‐charging and long cycle stability involved 8‐electron participation. This work exemplifies the importance of advanced design of the molecular scale engineering including modulated redox‐active sites and high stability towards for fast‐charging and long‐lifespan cell devices.