Huang Shiwen, Su Xinjian, Wu Yanzhen, Xiong Xiao-Gen, Liu Yiliu
South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology Guangzhou 510640 China
Sino-French Institute of Nuclear Engineering and Technology, Sun Yat-sen University Zhuhai 519082 China.
Chem Sci. 2022 Sep 13;13(38):11352-11359. doi: 10.1039/d2sc04196k. eCollection 2022 Oct 5.
Discovering efficient catalysts is highly desired in expanding the application of halogen-bonding catalysis. We herein report our findings on applying triaminocyclopropenium (TAC) iodides as highly potent catalysts for halogen-bonding catalyzed living radical polymerization. Promoted by the unique effect of ion-pair strain between the TAC cation and the iodide anion, the TAC iodides showed high catalytic efficiency in the halogen-bonding catalysis toward radical generation, and surpassed the previously reported organic iodide catalysts. With the TAC iodide as catalyst, radical polymerization with a living feature was successfully realized, which shows general applicability with a variety of monomers and produced block copolymers. In addition, the TAC-iodides also showed promising feasibility in catalyzing the radical depolymerization of iodo-terminated polymethacrylates. Noteworthily, the catalytic capacity of the TAC iodides is demonstrated to be closely related to the electronic properties of the TAC cation, which offers a molecular platform for further catalyst screening and optimization.
在拓展卤键催化的应用方面，人们迫切希望发现高效催化剂。我们在此报告了关于应用三氨基环丙烯鎓（TAC）碘化物作为卤键催化活性自由基聚合的高效催化剂的研究结果。受TAC阳离子与碘阴离子之间独特的离子对张力效应的促进，TAC碘化物在卤键催化自由基生成方面表现出高催化效率，超过了先前报道的有机碘化物催化剂。以TAC碘化物为催化剂，成功实现了具有活性特征的自由基聚合，该聚合对多种单体具有普遍适用性，并制备出了嵌段共聚物。此外，TAC碘化物在催化碘封端的聚甲基丙烯酸酯的自由基解聚方面也显示出有前景的可行性。值得注意的是，TAC碘化物的催化能力被证明与TAC阳离子的电子性质密切相关，这为进一步的催化剂筛选和优化提供了一个分子平台。
