Heterogeneous Solid-State Plasticity of a Multi-Functional Metallo-Supramolecular Shape-Memory Polymer towards Arbitrary Shape Programming.

Shape-memory polymers (SMPs) exhibit notable shape-shifting behaviors under environmental stimulations. In a specific shape-memory cycle, the material can be temporarily fixed at diverse geometries while recovering to the same permanent shape driven by the elastic network, which somewhat limits the versatility of SMPs. Via dynamic metallo-supramolecular interactions, herein, we report a multi-functional shape-memory polymer with tunable permanent shapes. The network is constructed by the metallic coordination of a four-armed polycaprolactone with a melting temperature of 54 °C. Owing to the thermo-induced stress relaxation through the bond exchange, the SMPs can be repeatedly programmed into different geometries in their solid state and show the self-welding feature. Via further welding of films crosslinked by different ions, it will present heterogeneous solid-state plasticity, and a more sophisticated shape can be created after the uniform thermal treatment. With elasticity and plasticity in the same network, the SMPs will display programmable shape-shifting behaviors. Additionally, the used material can be recast into a new film which retains the thermo-induced plasticity. Overall, we establish a novel strategy to manipulate the permanent shapes of SMPs through solid-state plasticity and develop a multi-functional shape-shifting material that has many practical applications.