Mechanochemical synthesis of an elusive fluorinated polyacetylene
Mechanochemical synthesis of an elusive fluorinated polyacetylene
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DOI：
10.1038/s41557-020-00608-8
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发表时间：
2020-12-22
期刊：
影响因子：
21.8
通讯作者：
Burns, Noah Z.
中科院分区：
文献类型：
--
作者：
Boswell, Benjamin R.;Mansson, Carl M. F.;Burns, Noah Z.
氟化聚乙炔通常被证明无法使用传统的聚合物合成方法获得，但人们对其预测的性能非常感兴趣。现在，机械化学解链策略已成功合成了金色的半导体氟化聚乙炔，与聚乙炔相比，其在空气中的稳定性更高。聚合物机械化学传统上用于研究机械力对聚合物主链内化学键的影响或生成力响应材料。通过化学转化聚合物，特别是通过其他方式无法获得的产品，它在大规模合成全新材料方面尚未得到充分利用。在这里，我们利用聚合物机械化学来合成氟化聚乙炔，这是一种长期寻求的空气稳定聚乙炔，但传统方法无法合成。我们通过四个化学步骤在克级上构建了单体，其中涉及氟原子在奇异光化学级联中的快速结合，其机制和精致的立体选择性是通过计算得知的。聚合后，通过超声波强制活化产生金色的半导体含氟聚合物。这项工作表明，聚合物机械化学是一种有价值的合成工具，可用于制备规模的材料。
Fluorinated polyacetylene has typically proven to be inaccessible using traditional polymer synthesis, but there is much interest in its predicted properties. Now, a mechanochemical unzipping strategy has succeeded in the synthesis of a gold-coloured, semiconducting fluorinated polyacetylene with improved stability in air compared to polyacetylene.Polymer mechanochemistry has traditionally been employed to study the effects of mechanical force on chemical bonds within a polymer backbone or to generate force-responsive materials. It is under-exploited for the scalable synthesis of wholly new materials by chemically transforming the polymers, especially products inaccessible by other means. Here we utilize polymer mechanochemistry to synthesize a fluorinated polyacetylene, a long-sought-after air-stable polyacetylene that has eluded synthesis by conventional means. We construct the monomer in four chemical steps on gram scale, which involves a rapid incorporation of fluorine atoms in an exotic photochemical cascade whose mechanism and exquisite stereoselectivity were informed by computation. After polymerization, force activation by ultrasonication produces a gold-coloured, semiconducting fluoropolymer. This work demonstrates that polymer mechanochemistry is a valuable synthetic tool for accessing materials on a preparative scale.