Institute of Organic Chemistry, University of Ulm, Ulm, Germany.
Department of Innovative Technologies, University of Applied Sciences and Arts of Southern Switzerland, Lugano-Viganello, Switzerland.
Nat Commun. 2021 May 25;12(1):3134. doi: 10.1038/s41467-021-23370-y.
The development of powerful methods for living covalent polymerization has been a key driver of progress in organic materials science. While there have been remarkable reports on living supramolecular polymerization recently, the scope of monomers is still narrow and a simple solution to the problem is elusive. Here we report a minimalistic molecular platform for living supramolecular polymerization that is based on the unique structure of all-cis 1,2,3,4,5,6-hexafluorocyclohexane, the most polar aliphatic compound reported to date. We use this large dipole moment (6.2 Debye) not only to thermodynamically drive the self-assembly of supramolecular polymers, but also to generate kinetically trapped monomeric states. Upon addition of well-defined seeds, we observed that the dormant monomers engage in a kinetically controlled supramolecular polymerization. The obtained nanofibers have an unusual double helical structure and their length can be controlled by the ratio between seeds and monomers. The successful preparation of supramolecular block copolymers demonstrates the versatility of the approach.
发展强大的方法对于活体共价聚合一直是有机材料科学进步的关键驱动力。虽然最近有关于活体超分子聚合的显著报道，但单体的范围仍然很窄，而且这个问题的简单解决方案还难以捉摸。在这里，我们报告了一种基于全顺式 1,2,3,4,5,6-六氟环己烷独特结构的用于活体超分子聚合的最小分子平台，这是迄今为止报道的最极性脂肪族化合物。我们利用这个大偶极矩（6.2 德拜）不仅可以热力学上驱动超分子聚合物的自组装，还可以产生动力学捕获的单体状态。在加入定义明确的种子后，我们观察到休眠单体参与了动力学控制的超分子聚合。所得的纳米纤维具有不寻常的双螺旋结构，其长度可以通过种子和单体之间的比例来控制。成功制备的超分子嵌段共聚物证明了该方法的多功能性。
