title: Facile Construction of Metallo-supramolecular Poly(3-hexylthiophene)-block-Poly(ethylene oxide) Diblock Copolymers via Complementary Coordination and Their Self-Assembled Nanostructures.
abstract: Complementary coordination of two predesigned 2,2':6',2″-terpyridine-based ligands to a ZnIIion 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 ZnII-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.
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors.forename: Yun-Jui
authors.initials: YJ
authors.lastname: He
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors.forename: Tsung-Han
authors.initials: TH
authors.lastname: Tu
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors.forename: Ming-Kun
authors.initials: MK
authors.lastname: Su
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors.forename: Chia-Wei
authors.initials: CW
authors.lastname: Yang
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors.forename: Kien Voon
authors.identifier: 0000-0002-5910-6497
authors.initials: KV
authors.lastname: Kong
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors.forename: Yi-Tsu
authors.identifier: 0000-0001-9658-2188
authors.initials: YT
authors.lastname: Chan