Wang Jia, Bai Tianwen, Chen Yue, Ye Canbin, Han Ting, Qin Anjun, Ling Jun, Tang Ben Zhong
State Key Laboratory of Luminescent Materials and Devices, Center for Aggregation-Induced Emission, South China University of Technology, Guangzhou 510640, China.
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China.
ACS Macro Lett. 2019 Sep 17;8(9):1068-1074. doi: 10.1021/acsmacrolett.9b00448. Epub 2019 Aug 13.
The C-H activation has been a hot research area in organic chemistry, and the most difficult one is the C(sp)-H activation. Although the C-H activation has been introduced to the research of synthetic polymer chemistry, the polymerization developed based on C(sp)-H activation is rarely reported, which will enrich the tools for the preparation of functional polymers. In this work, palladium/benzoic acid catalyzed polymerization of internal diynes and diols through C(sp)-H activation was successfully established. Regio- and stereoregular functional poly(allylic ether)s with 100% -isomers and high weight average molecular weights ( up to 33200) were prepared in excellent yield (98%). The reaction mechanism was unveiled with the assistance of density functional theory calculations. Furthermore, the thin films of polymers display high refractive indices and low optical dispersions. The polymer containing tetraphenylethene moiety displays the aggregation-enhanced emission feature and could be used to generate 2D fluorescent photopattern. Thus, this work not only establishes a powerful polymerization based on C(sp)-H activation, but also furnishes functional polymers for diverse applications.
碳氢活化一直是有机化学领域的研究热点，其中最难的是C(sp) - H活化。尽管碳氢活化已被引入到合成高分子化学的研究中，但基于C(sp) - H活化发展起来的聚合反应却鲜有报道，而这将丰富功能性聚合物的制备手段。在这项工作中，成功建立了钯/苯甲酸催化内二炔和二醇通过C(sp) - H活化的聚合反应。以优异的产率（98%）制备了区域和立体规整的官能化聚（烯丙基醚），其具有100%的 - 异构体和高重均分子量（高达33200）。借助密度泛函理论计算揭示了反应机理。此外，聚合物薄膜表现出高折射率和低光学色散。含有四苯乙烯基团的聚合物具有聚集诱导发光特性，可用于生成二维荧光图案。因此，这项工作不仅建立了一种基于C(sp) - H活化的强大聚合反应，还提供了用于多种应用的功能性聚合物。
