A Thermally‐Processable Conductive Supramolecular Metallacage Decorated with Polyethylene Glycol Chains for Self‐Healable and Recyclable Electronics

ABSTRACT Supramolecular coordination complexes (SCCs) possess precise molecular architectures attractive for catalysis, sensing, and nanomedicine, yet their thermal processing into bulk materials is severely hindered by strong π–π stacking interactions, typically restricting them to solution, gel, or particulate forms. Herein, this study reports a thermally‐processable metallacage TPMc, decorated with six polyethylene glycol chains (PEG) that overcome this fundamental limitation. PEG chains act as a “molecular lubricant” that disrupts intermolecular forces and expands intermolecular distances, endowing TPMc with thermal processability that enables thermal fabrication for free‐standing bulk materials with various shapes while simultaneously maintaining self‐healing and reprocessing capabilities without structural degradation. As proof of application, TPMc bulk material was employed as an ionic conductor for ultrasensitive thermal sensing, which exhibited an ultrahigh thermal response (3294.9% at 60°C) and remained functional even after damage or reconfiguration. This work overcomes the processing barrier of SCCs, expands their potential in recyclable electronics, and paves the way for broader practical applications of SCCs‐based bulk materials.