Journal
POLYMERS
Volume 12, Issue 12, Pages -Publisher
MDPI
DOI: 10.3390/polym12122842
Keywords
metallo-initiator; terpyridine; heteroleptic complexation; self-assembly; metallo-supramolecular copolymer
Categories
Funding
- Ministry of Science and Technology of Taiwan [MOST 109-2113-M-002-019-MY3]
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Complementary 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 alpha-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 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 by H-1 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.
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