Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology , Guangzhou 510640, China.
Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology , Clear Water Bay, Kowloon, Hong Kong, China.
J Am Chem Soc. 2017 Apr 19;139(15):5437-5443. doi: 10.1021/jacs.7b00929. Epub 2017 Apr 7.
Efficient synthesis of poly(enamine)s has been a great challenge because of their poor stability, poor solubility, and low molecular weights. In this work, a spontaneous amino-yne click polymerization for the efficient preparation of poly(enamine)s was established, which could proceed with 100% atom efficiency under very mild conditions without any external catalyst. Through systematic optimization of the reaction conditions, several soluble and thermally stable poly(β-aminoacrylate)s with high molecular weights (M up to 64400) and well-defined structures were obtained in excellent yields (up to 99%). Moreover, the polymerization can perform in a regio- and stereospecific fashion. Nuclear magnetic resonance spectra analysis revealed that solely anti-Markovnikov additive products with 100% E-isomer were obtained. The reaction mechanism was well demonstrated with the assistance of density functional theory calculations. In addition, by introducing the tetraphenylethene moiety, the resulting polymers exhibit unique aggregation-induced emission characteristics and could be applied in explosives detection and bioimaging. This polyhydroamination is a new type of click polymerization and opens up enormous opportunities for preparing functional polymeric materials.
高效合成聚（烯胺）一直是一个巨大的挑战，因为它们的稳定性差、溶解度低、分子量低。在这项工作中，建立了一种自发的氨基-炔点击聚合反应，可在非常温和的条件下以 100%的原子效率进行，无需任何外部催化剂。通过对反应条件的系统优化，在优异的收率（高达 99%）下，获得了几种可溶性和热稳定的高分子量（高达 64400）和结构明确的聚（β-丙烯酰胺）。此外，聚合可以以区域和立体特异性的方式进行。核磁共振谱分析表明，仅获得了具有 100% E-异构体的反-Markovnikov 加合物。反应机理通过密度泛函理论计算得到了很好的证明。此外，通过引入四苯乙烯部分，所得聚合物表现出独特的聚集诱导发射特性，可应用于爆炸物检测和生物成像。这种多氢胺化反应是一种新型的点击聚合反应，为制备功能性聚合材料开辟了巨大的机会。
