Fukui Tomoya, Sasaki Norihiko, Takeuchi Masayuki, Sugiyasu Kazunori
Molecular Design & Function Group , National Institute for Materials Science (NIMS) , 1-2-1 Sengen , Tsukuba , Ibaraki 305-0047 , Japan . Email:
Department of Materials Physics and Chemistry , Graduate School of Engineering , Kyushu University , 744 Moto-oka, Nishi-ku , Fukuoka 819-0395 , Japan.
Chem Sci. 2019 Jul 1;10(28):6770-6776. doi: 10.1039/c9sc02151e. eCollection 2019 Jul 28.
Although living supramolecular polymerization (LSP) has recently been realized, the scope of the monomer structures applicable to the existing methods is still limited. For instance, a monomer that spontaneously nucleates itself cannot be processed in a manner consistent with LSP. Herein, we report a new method for such a "reactive" monomer. We use a 'dummy' monomer which has a similar structure to the reactive monomer but is incapable of one-dimensional supramolecular polymerization. We show that in the presence of the dummy monomer, the reactive monomer is kinetically trapped in the dormant state. In this way, spontaneous nucleation of the reactive monomer is retarded; yet, addition of seeds of a supramolecular polymer can initiate the supramolecular polymerization in a chain growth manner. As a result, we obtain the supramolecular polymer of the reactive monomer with a controlled length, which is otherwise thermodynamically inaccessible. We believe that this concept will expand the scope of LSP for the synthesis of other functional supramolecular polymers, and thus lead to a variety of applications.
尽管近年来已经实现了活性超分子聚合（LSP），但适用于现有方法的单体结构范围仍然有限。例如，一种能自发成核的单体无法以与LSP一致的方式进行处理。在此，我们报道了一种针对这种“活性”单体的新方法。我们使用一种“虚拟”单体，其结构与活性单体相似，但不能进行一维超分子聚合。我们表明，在虚拟单体存在的情况下，活性单体在动力学上被困于休眠状态。通过这种方式，活性单体的自发成核受到抑制；然而，添加超分子聚合物的晶种可以以链增长的方式引发超分子聚合。结果，我们获得了具有可控长度的活性单体超分子聚合物，否则该聚合物在热力学上是无法获得的。我们相信，这一概念将扩大LSP在合成其他功能性超分子聚合物方面的范围，从而带来各种应用。
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