基于C–H活化的炔烃聚合反应合成多功能稠(杂)环聚合物

Synthesis of multifunctional fused(hetero)cyclic polymers by alkynebased polyannulations through C–H activation

稠(杂)环聚合物是一类重要的功能聚合物,因其优异的光电特性而被广泛应用于光电领域.这类聚合物的传统制备方法往往需要用到修饰有复杂官能团的稠(杂)环单体,这些单体种类有限且合成难度大,导致稠(杂)环聚合物的发展受到限制. C–H活化过程的发现与提出为利用惰性的C–H键作为潜在官能团提供了可能,有效避免了对单体进行复杂修饰的要求,大大扩增了单体的种类和来源.基于C–H活化的炔烃环化聚合反应,能够在聚合物骨架中原位直接形成稠(杂)环结构,具有原料简单易得、聚合效率高、产物结构丰富等诸多优势,因此受到广泛关注.本文分类总结了基于C–H活化的炔烃环化聚合领域的最新进展,包括合成手段和所得聚合物的性质与功能介绍,并对该领域的未来发展方向进行了展望.

Fused(hetero)cyclic polymers are important functional polymers with wide applications in photoelectronic fields due to their unique photophysical properties. However, traditional synthetic methods toward such polymers normally require limited and expensive fused aromatic substrates, elaborate reaction control, complicated operation procedures, and painful isolation. These synthetic difficulties greatly restrict their accessibility. C–H-activated polyannulations of acetylenic monomers offer a facile and efficient way for the synthesis of fused(hetero)cyclic polymers by utilizing inert C–H as potential functional groups. With this strategy, complex fused(hetero)cycles can be generated in-situ in polymer backbones from simple and readily available reactants. Herein, recent progress on alkynebased polyannulations derived from C–H activated reactions will be summarized with representative examples. The properties and functionalities of the obtained fused(hetero)cyclic polymers will also be introduced.