Structure and Properties of Metallosupramolecular Polymers with a Nitrogen-Based Bidentate Ligand.

The solid-state properties of supramolecular polymers that feature metal-ligand (ML) complexes are, in addition to the general nature of the monomer, significantly affected by the choice of ligand and metal salt. Indeed, the variation of these components can be used to alter the structural, thermal, mechanical, and viscoelastic properties over a wide ranges. Moreover, the dynamic nature of certain ML complexes can render the resulting metallosupramolecular polymers (MSPs) stimuli-responsive, enabling functions such as healing, reversible adhesion, and mechanotransduction. We here report MSPs based on the bidentate ligand 6-(1'-methylbenzimidazolyl) pyridine (MBP), which is easily accessible and forms threefold coordination complexes with various transition metal ions. Thus, a poly(ethylene--butylene) telechelic was end-functionalized with two MBP ligands and the resulting macromonomer was assembled with the triflate salts of either Zn, Fe, or Ni. All three MSPs microphase separate and adopt, depending on the metal ion and thermal history, lamellar or hexagonal morphologies with crystalline domains formed by the ML complexes. The melting transitions are well below 200 °C, and this permits facile (re)processing. Furthermore, defects can be readily and fully healed upon exposure to UV-light. While the three MSPs display similar moduli in the rubbery regime, their extensibility and tensile strength depend on the nature of the ML complex, which similarly affects the long-range order and dynamic behavior.