Li Shun-Shun, Zhu Nengbo, Jing Ya-Nan, Li Yajun, Bao Hongli, Wan Wen-Ming
State Key Laboratory of Structural Chemistry, Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 West Yangqiao Road, Fuzhou 350002, P. R. of China; University of Chinese Academy of Sciences, Beijing 100049, P. R. of China; State Key Laboratory of Heavy Oil Processing and Center for Bioengineering and Biotechnology, China University of Petroleum (East China), 66 West Changjiang Road, Qingdao 266580, P. R. of China.
State Key Laboratory of Structural Chemistry, Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 West Yangqiao Road, Fuzhou 350002, P. R. of China; University of Chinese Academy of Sciences, Beijing 100049, P. R. of China.
iScience. 2020 Apr 24;23(4):101031. doi: 10.1016/j.isci.2020.101031. Epub 2020 Apr 5.
Carbon-carbon bond formation through polarity reversal ketyl radical anion coupling of carbonyls has inspired new reaction modes to this cornerstone carbonyl group and played significant roles in organic chemistry. The introduction of this resplendent polarity reversal ketyl strategy into polymer chemistry will inspire new polymerization mode with unpredicted discoveries. Here we show the successful introduction of polarity reversal ketyl approach to polymer chemistry to realize self-condensing ketyl polymerization with polymerization-induced emission. In this polarity reversal approach, it exhibits intriguing reversed polymerizability, where traditional excellent leaving groups are not suitable for polymerization but challenging polymerizations involving the cleavage of challenging C-F and C-CF bonds are realized under mild Barbier conditions. This polarity reversal approach enables the polymer chemistry with polarity reversal ketyl mode, opens up a new avenue toward the polymerization of challenging C-X bonds under mild conditions, and sparks design inspiration of new reaction, polymerization, and functional polymer.
通过羰基的极性反转酮基自由基阴离子偶联形成碳-碳键，为这一基础羰基基团带来了新的反应模式，并在有机化学中发挥了重要作用。将这种出色的极性反转酮基策略引入聚合物化学中，将激发新的聚合模式，并带来意想不到的发现。在此，我们展示了将极性反转酮基方法成功引入聚合物化学，以实现具有聚合诱导发光的自缩合酮基聚合。在这种极性反转方法中，它展现出有趣的反向聚合性，即传统的优良离去基团不适合聚合反应，但在温和的巴比耶条件下，涉及具有挑战性的C-F键和C-CF键断裂的挑战性聚合反应得以实现。这种极性反转方法实现了具有极性反转酮基模式的聚合物化学，为在温和条件下实现具有挑战性的C-X键的聚合开辟了一条新途径，并激发了新反应、聚合反应和功能聚合物的设计灵感。
