Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock Copolymers
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) bi...
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| Format: | Article |
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MDPI AG
2020-11-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/12/12/2842 |
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| author | Tsung-Han Tu Yi-Tsu Chan |
| author_facet | Tsung-Han Tu Yi-Tsu Chan |
| author_sort | Tsung-Han Tu |
| collection | DOAJ |
| description | 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 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)-<i>block</i>-PS diblock copolymers were prepared by simply mixing the corresponding terminally tpy-modified homopolymers with Zn(II) ions, and further characterized by <sup>1</sup>H 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. |
| first_indexed | 2024-03-10T14:28:02Z |
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| id | doaj.art-3e503ec66c13453cb37340d9c7cf009c |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T14:28:02Z |
| publishDate | 2020-11-01 |
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| series | Polymers |
| spelling | doaj.art-3e503ec66c13453cb37340d9c7cf009c2023-11-20T22:49:43ZengMDPI AGPolymers2073-43602020-11-011212284210.3390/polym12122842Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock CopolymersTsung-Han Tu0Yi-Tsu Chan1Department of Chemistry, National Taiwan University, Taipei 10617, TaiwanDepartment of Chemistry, National Taiwan University, Taipei 10617, TaiwanComplementary 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)-<i>block</i>-PS diblock copolymers were prepared by simply mixing the corresponding terminally tpy-modified homopolymers with Zn(II) ions, and further characterized by <sup>1</sup>H 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.https://www.mdpi.com/2073-4360/12/12/2842metallo-initiatorterpyridineheteroleptic complexationself-assemblymetallo-supramolecular copolymer |
| spellingShingle | Tsung-Han Tu Yi-Tsu Chan Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock Copolymers Polymers metallo-initiator terpyridine heteroleptic complexation self-assembly metallo-supramolecular copolymer |
| title | Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock Copolymers |
| title_full | Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock Copolymers |
| title_fullStr | Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock Copolymers |
| title_full_unstemmed | Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock Copolymers |
| title_short | Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-<i>b</i>-PS Diblock Copolymers |
| title_sort | synthesis of terpyridine end modified polystyrenes through atrp for facile construction of metallo supramolecular p3ht i b i ps diblock copolymers |
| topic | metallo-initiator terpyridine heteroleptic complexation self-assembly metallo-supramolecular copolymer |
| url | https://www.mdpi.com/2073-4360/12/12/2842 |
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