A rational strategy for the realization of chain-growth supramolecular polymerization
A rational strategy for the realization of chain-growth supramolecular polymerization
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DOI：
10.1126/science.aaa4249
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发表时间：
2015-02-06
期刊：
影响因子：
56.9
通讯作者：
Aida, Takuzo
中科院分区：
文献类型：
--
作者：
Kang, Jiheong;Miyajima, Daigo;Aida, Takuzo
在过去的十年中，超分子聚合的重大进展对功能软材料的设计产生了实质性的影响。然而，尽管最近的进展，大多数研究仍然是基于一个先入为主的概念，即超分子聚合遵循一个逐步增长的机制，这排除了控制链长，序列和立体化学结构。在这里，我们报告链增长聚合的实现，通过设计亚稳单体与形状促进分子内氢键网络。单体在环境温度下的自发聚合在构象上受到限制，但在与定制的引发剂混合时开始以典型的活性机理的特征聚合。链增长发生立体选择性，因此能够实现外消旋单体的光学拆分。
Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer.