Supramolecular Engineering of a Homo[2]catenane Filler Enables Polymer Composites with Exceptional High-Temperature Capacitive Energy Storage

The escalating demand for high-performance dielectric energy storage materials in pulse-power systems and portable electronics calls for polymer film capacitors with high discharged energy density and breakdown strength. Conventional polymers, however, suffer severe performance degradation under concurrent thermal and electrical stress, and existing reinforcement strategies—involving inorganic nanofillers or chemical crosslinking—often compromise flexibility, introduce interfacial defects, or involve complex processing. Herein, we demonstrate that incorporating a rigid mechanically interlocked molecule, specifically an octacationic homo[2]catenane, into a polyimide matrix yields robust, crosslink-like networks through strong [π∙∙∙π] electrostatic interaction between electron-rich aromatic units of polyimide and electron-deficient homo[2]catenane. This supramolecular network simultaneously enhances breakdown strength via densified chain packing and suppresses conduction loss by forming deep electron traps derived from the high electron affinity of homo[2]catenane. The optimized PI–HC8+ composite achieves a high discharged energy density of 7.86 J/cm3 with an efficiency > 80% and sustains stable performance over 105 charge–discharge cycles at 150 °C. This research establishes mechanically interlocked molecules as a new class of functional fillers for high-performance polymer dielectrics, opening an unexplored avenue in the design of next-generation capacitive energy-storage materials.