Facile Construction of Metallo-supramolecular Poly(3-hexylthiophene)-block-Poly(ethylene oxide) Diblock Copolymers via Complementary Coordination and Their Self-Assembled Nanostructures

Complementary coordination of two predesigned 2,2′:6′,2″-terpyridine-based ligands to a Zn^II ion led to the exclusive formation of a heteroleptic bis­(terpyridine) complex under ambient conditions. This highly self-selective process was facilitated by 9-anthracenyl substituents at the 6,6″-positions of a terpyridine, which not only decelerated the formation rate of its homoleptic complex, but also provided π-stacking stabilization in the heteroleptic complex. Facile construction of metallo-supramolecular poly­(3-hexylthiophene) (P3HT)-block-poly­(ethylene oxide) (PEO) diblock copolymers was realized using the complementary ligand pair. The morphological studies of the amphiphilic block copolymers in solution were conducted by atomic force microscopy and transmission electron microscopy, indicating that the self-assembled core–shell morphology such as spherical and fibrillar nanostructures could be controlled by adjusting the rod–coil block ratios. The heteroleptic complexes residing at the junction between two polymer blocks could be readily dissociated by EDTA to afford the unshelled P3HT nanofiber networks, and restored by treatment of bifunctional Zn^II-terpyridine-capped PEO to redisperse the aggregates. The presented supramolecular methodology highlights the merits of complementary metal–ligand coordination, and offers a new approach to engineering nanostructures assembled from rod–coil block copolymers.