An asymmetric A-B-A' metallo-supramolecular triblock copolymer linked by Ni(2+)-bis-terpyridine complexes at one junction.

A metallo-supramolecular triblock copolymer polystyrene-b-polyisoprene-[Ni(2+)]-polystyrene (SI-[Ni(2+)]-S') has been efficiently prepared using a one-pot, two-step procedure, where the blocks are held by bis-terpyridine complexes at the junction of SI-S'. This specific metallo-supramolecular chemistry is demonstrated to be a robust approach to potentially broaden the diversity of block copolymers. The location of the metal-ligand complexes has a profound influence on the phase separation of the triblock copolymer in the bulk, which results in a distinctive phase segregation between the end blocks and leads to an unexpected asymmetry of the triblock copolymer. The metal-ligand complexes are found to be preferentially located on the adjacent spherical domain and form a core-shell structure. The resulting multiphase material exhibits distinct elastomeric properties with significant toughness and creep recovery behavior. This type of triblock copolymer is anticipated to be a novel class of hybrid thermo-plastic elastomeric material with wide tunability and functionality.