Integrated Extrinsic and Intrinsic Self‐Healing of Polysiloxane Materials by Cleavable Molecular Cages Encapsulating Fluoride Ions

Self‐healing ability is crucial to increasing the lifetime and reliability of materials. In this study, spatiotemporal control of the healing of a polysiloxane material is achieved using a cleavable cage compound encapsulating a fluoride ion (F(−)), which triggeres the dynamic rearrangement of the siloxane (Si–O–Si) networks. A self‐healing siloxane‐based elastomer is prepared by cross‐linking polydimethylsiloxane (PDMS) with a F(−)‐encapsulating cage‐type germoxane (Ge–O–Ge) compound. This material can self‐heal repeatedly under humid conditions. The F(−) released by hydrolytic cleavage of the cage framework contributes to rejoining of the cut pieces by promoting the local rearrangement of the siloxane networks. The use of a molecular cage encapsulating a catalyst for dynamic bond rearrangement provides a new concept for designing self‐healing polysiloxane materials based on integrated extrinsic and intrinsic mechanisms.