Department of Chemistry and Research Institution of Natural Sciences, Gyeongsang National University (GNU), Jinju, 52828, Republic of Korea.
Angew Chem Int Ed Engl. 2023 Jun 19;62(25):e202300913. doi: 10.1002/anie.202300913. Epub 2023 Mar 28.
We report the unique synthesis of chiral supramolecular tri- and penta-BCPs with controllable chirality using kinetically adjusted seeded supramolecular copolymerization in THF and DMSO (99 : 1, v/v). Tetraphenylethylene (d- and l-TPE) derivatives bearing d- and l-alanine side chains formed thermodynamically favored chiral products via a kinetically trapped in monomeric state with a long lag phase. In contrast, achiral TPE-G containing glycine moieties did not form a supramolecular polymer owing to the energy barrier in its kinetically trapped state. We show that the copolymerization of the metastable states of TPE-G not only enables the generation of supramolecular BCPs by the seeded living growth method, but also transfers chirality at the seed ends. This research demonstrates the generation of chiral supramolecular tri- and penta-BCPs with B-A-B, A-B-A-B-A, and C-B-A-B-C block patterns accompanying chirality transfer via seeded living polymerization.
我们报告了使用动力学调节的种子超分子共聚在 THF 和 DMSO（99:1，v/v）中可控手性合成手性超分子三嵌段和五嵌段共聚物的独特方法。带有 d-和 l-丙氨酸侧链的四苯乙烯（d-和 l-TPE）衍生物通过在单体状态下动力学捕获并具有长滞后相形成热力学有利的手性产物。相比之下，由于其动力学捕获状态的能垒，不含手性 TPE-G 的甘氨酸部分不能形成超分子聚合物。我们表明，TPE-G 的亚稳态共聚不仅能够通过种子活性生长方法生成超分子嵌段共聚物，而且还可以在手性种子端转移手性。这项研究证明了通过种子活性聚合生成具有 B-A-B、A-B-A-B-A 和 C-B-A-B-C 嵌段模式的手性超分子三嵌段和五嵌段共聚物，同时伴随手性转移。
