Two-dimensional covalent organic frameworks (2D-COFs) represent an attractive platform for organic electrodes, yet they suffer from inferior power capability caused by poor Li⁺ intercalation in densely π-π stacked interlayers. Herein, featuring nonplanar π-conjugated heteroaromatic linkages, phenothiazine with “butterfly” conformation is integrated as a structural scaffold to instantly tune packing topology and interplanar distance. Corrugated 2D-COF maintaining aromaticity and crystallinity is formed with good electroactivity, enlarged d-spacing, and accessibility to interior Li⁺-interactive sites, which results in remarkable capacity of 220–773 mAh g⁻¹ at high rates ranging from 100 to 3,200 mA g⁻¹ with a good cycle life, bridging the performance gap between power and energy. Mechanistic studies reveal a dual storage mechanism with dominating capacitive storage promoted by π-Li⁺ interactions, as well as enhanced redox activity of carbonyls for better chemical accessibility. These findings elucidate inherent effects of molecular-level d-spacing regulation enabled by heteroaromatics, presenting a new design concept of interlayer engineering for organic porous energy storage materials.

二维共价有机框架 (2D-COF) 代表了有机电极的一个有吸引力的平台，但由于 Li ⁺在密集的 π-π 堆叠夹层中的嵌入不良，它们的功率能力较差。在此，具有非平面 π- 共轭杂芳基键，具有“蝴蝶”构象的吩噻嗪被集成为结构支架，以立即调整堆积拓扑和面间距离。形成保持芳香性和结晶性的波纹状 2D-COF，具有良好的电活性、更大的 d 间距和内部 Li ⁺相互作用位点的可及性，导致在100 至 3,200 的高倍率下具有 220–773 mAh g ⁻¹的显着容量毫安·克^-1具有良好的循环寿命，弥合了功率和能量之间的性能差距。^{机理研究揭示了由 π-Li +}相互作用促进的主导电容存储的双重存储机制，以及增强的羰基氧化还原活性以获得更好的化学可及性。这些发现阐明了杂芳烃分子水平 d 间距调控的内在效应，提出了有机多孔储能材料层间工程的新设计理念。