Repairable, Recyclable, and Regenerable Macrocycle Organic Polymer†

Comprehensive Summary Covalent/metal organic frameworks are highly attractive due to their tunable structure and properties, and broad applications in multiple fields. However, they still suffer from numbers of drawbacks including low solubility, harsh synthesis and fabrication, and low mechanical flexibility. Herein, we report a new organic framework consisting of macrocycles and organic frames in its periodic structure, and denote it as macrocycle organic polymer (MOP). The size‐tunable macrocycles containing peripheral furan units are synthesized by anionic ring‐opening polymerization, which undergo a reversible Diels‐Alde reaction with bismaleimide to generate/degrade MOPs at given temperatures. Relying on above features, MOPs exhibit excellent flexibility, healable ability and recycle ability. Interestingly, owing to the “living” nature of anionic ring‐opening polymerization, MOPs can self‐grow into bigger sizes in the presence of monomer and catalysis, analogs to the living creatures. Moreover, their high porosity and rich thioether structure enable them as good metal ion absorbers and promising applications in wearable electronics.