Synthesis and Characterization of Metallopolymer Networks Featuring Triple Shape-Memory Ability Based on Different Reversible Metal Complexes

This study presents the synthesis and characterization of metallopolymer networks with a triple shape-memory ability. A covalently crosslinked polymer network featuring two different additional ligands in its side chains is synthesized via free radical polymerization (FRP). The subsequent addition of different metal salts leads to the selective formation of complexes with two different association constants (<i>K_a</i>), proven via isothermal titration calorimetry (ITC). Those two supramolecular crosslinks feature different activation temperatures and can act as two individual switching units enabling the fixation and recovery of two temporary shapes. The presented samples were investigated in a detailed fashion via differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and FT-Raman spectroscopy. Furthermore, thermo-mechanical analyses (TMA) revealed excellent dual and triple shape-memory abilities of the presented metallopolymer networks.