Supramolecular mimics of phase separating covalent diblock copolymers

In this study, we explore the supramolecular association and phase separation properties of non-covalent analogues of polystyrene-b-polyethylene glycol (PS-b-PEG) and polystyrene-b-polyisoprene (PS-b-PI) diblock copolymers. For this purpose, a PS homopolymer is end-functionalized with a quadruple hydrogen bonding unit and PEG and PI homopolymers are end-functionalized with a hetero-complementary hydrogen bonding group. Hetero-dimerization between the complementary chain ends of the respective homopolymers furnishes supramolecular (s) PS-s-PEG and PS-s-PI diblock copolymers with phase-separation studies in thin films and bulk demonstrating that the non-covalent block copolymers are capable of self-organizing into nanostructured morphologies reminiscent of their covalent analogues.