Tu T.-HYI-TSU CHAN2021-08-032021-08-03202020734360https://www.scopus.com/inward/record.uri?eid=2-s2.0-85096779815&doi=10.3390%2fpolym12122842&partnerID=40&md5=5939a04d2091be70654e57a8b57b27fbhttps://scholars.lib.ntu.edu.tw/handle/123456789/575888Complementary complexation between 2,2′:6′,2”-terpyridine (tpy) and 6,6”-dianthracenyl-substituted tpy in the presence of Zn(II) ions provided an efficient strategy for construction of metallo-supramolecular diblock copolymers. To synthesize well-defined tpy-modified polystyrenes (PSs), an Fe(II) bis(tpy) complex bearing α-bromoester as a metallo-initiator was applied to atom transfer radical polymerization (ATRP) to avoid poisoning the Cu(I) catalyst. Subsequently, a series of tpy-functionalized PSs was obtained after the decomplexation of <tpy-Fe(II)-tpy> junction by tetrakis(triethylammonium) ethylenediaminetetraacetate (TEA-EDTA) under mild conditions. The metallo-supramolecular poly(3-hexylthiophene) (P3HT)-block-PS diblock copolymers were prepared by simply mixing the corresponding terminally tpy-modified homopolymers with Zn(II) ions, and further characterized by1H NMR and diffusion ordered spectroscopy (DOSY) experiments. The approach using metallo-initiators for ATRP offers an opportunity to construct tpy-functionalized polymers with controllable molecular weights and low polydispersities. Through the spontaneous heteroleptic complexation, a variety of metallo-supramolecular diblock copolymers with tunable block ratios can be easily constructed. ? 2020 by the authors. Licensee MDPI, Basel, Switzerland.Atom transfer radical polymerization; Block copolymers; Catalyst poisoning; Copper compounds; Free radical reactions; Metals; Polydispersity; Polystyrenes; Supramolecular chemistry; Tea; Zinc compounds; Zinc metallography; Complementary complexation; Decomplexations; Diffusion ordered spectroscopies; Efficient strategy; Functionalized; Functionalized polymers; Metallo-supramolecular; Poly-3-hexylthiophene; Iron compoundsjournal article10.3390/polym121228422-s2.0-85096779815