Nickel(II)-catalyzed living polymerization of diazoacetates toward polycarbene homopolymer and polythiophene-block-polycarbene copolymers.
Nickel(II)-catalyzed living polymerization of diazoacetates toward polycarbene homopolymer and polythiophene-block-polycarbene copolymers.
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镍(II)催化重氮乙酸酯活性聚合制备聚卡宾均聚物和聚噻吩嵌段聚卡宾共聚物
DOI：
10.1038/s41467-022-28475-6
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发表时间：
2022-02-10
影响因子：
16.6
通讯作者：
Wu ZQ
中科院分区：
文献类型：
--
作者：
Zhou L;Xu L;Song X;Kang SM;Liu N;Wu ZQ
重氮乙酸酯聚合引起了广泛的研究关注，因为它是制造碳-碳（C-C）主链聚合物的有效方法。然而，基于廉价催化剂的重氮乙酸酯聚合一直是一个长期存在的挑战。在此，我们报道了一种Ni（II）催化剂，它可以促进各种重氮乙酸酯的活性聚合，产生明确的C-C主链聚合物，聚卡宾，具有可预测的分子量（Mn）和低分散性（Mw/Mn）。此外，Ni(II)催化的噻吩和重氮乙酸酯单体的连续活性聚合提供了有趣的π-共轭聚(3-己基噻吩)-嵌段聚卡宾共聚物，其产率高，Mn受控，组成可变，Mw/Mn低，尽管两种单体的结构和聚合机理不同。利用这种策略，可以轻松制备包含疏水性聚（3-己基噻吩）和亲水性聚卡宾嵌段的两亲性嵌段共聚物，并将其自组装成具有可调谐光致发光的明确的超分子结构。使用廉价催化剂进行重氮乙酸酯聚合一直是一个长期存在的挑战。作者在这里报道了一种 Ni(II) 催化剂，它可以促进各种重氮乙酸酯的活性聚合，产生明确的碳-碳主链聚合物，即聚卡宾。
Diazoacetate polymerization has attracted considerable research attention because it is an effective approach for fabricating carbon–carbon (C–C) main chain polymers. However, diazoacetate polymerization based on inexpensive catalysts has been a long-standing challenge. Herein, we report a Ni(II) catalyst that can promote the living polymerization of various diazoacetates, yielding well-defined C–C main chain polymers, polycarbenes, with a predictable molecular weight (Mn) and low dispersity (Mw/Mn). Moreover, the Ni(II)-catalyzed sequential living polymerization of thiophene and diazoacetate monomers affords interesting π-conjugated poly(3-hexylthiophene)-block-polycarbene copolymers in high yields with a controlled Mn, variable compositions, and low Mw/Mn, although the structure and polymerization mechanism of the two monomers differ. Using this strategy, amphiphilic block copolymers comprising hydrophobic poly(3-hexylthiophene) and hydrophilic polycarbene blocks are facilely prepared, which were self-assembled into well-defined supramolecular architectures with tunable photoluminescence. Diazoacetate polymerizations using inexpensive catalysts has been a long-standing challenge to achieve. Here the authors report a Ni(II) catalyst that can promote living polymerization of various diazoacetates, yielding well-defined carbon–carbon main chain polymers, polycarbenes.
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影响因子：
15
作者：
Fukui, Tomoya;Garcia-Hernandez, J. Diego;Manners, Ian
通讯作者：
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影响因子：
12.9
作者：
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影响因子：
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作者：
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通讯作者：
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影响因子：
--
作者：
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通讯作者：
Theato, Patrick