Developing nonconjugated materials with large Stokes shifts is highly desired. In this work, three kinds of hyperbranched aggregation-induced emission (AIE) polymers with tunable n/π electronic effects were synthesized. HBPSi-CBD contains alkenyl groups in the backbone and possesses a promoted n−π* transition and red-shifted emission wavelength with a large Stokes shift of 186 nm. Experiments and theoretical simulations confirmed that the planar π electrons in the backbone are responsible for the red-shifted emission due to the strong through-space n···π interactions and restricted backbone motions. Additionally, the designed HBPSi-CBD could be utilized as an ROS scavenger after coupling with l-methionine. The HBPSi-Met exhibits remarkable ROS scavenging properties with a scavenging capacity of 77%. This work not only gains further insight into the structure–property relationship of nonconjugated hyperbranched AIE polymers but also provides a promising ROS-scavenging biomaterial for the treatment of ROS-related diseases.

中文翻译：

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超支化聚集诱导发射聚合物中活性氧清除光物理行为的调控

非常需要开发具有大斯托克斯位移的非共轭材料。在这项工作中，合成了三种具有可调n/π电子效应的超支化聚集诱导发射（AIE）聚合物。 HBPSi-CBD 在主链中含有烯基，并具有促进的 n−π* 跃迁和红移发射波长，斯托克斯位移高达 186 nm。实验和理论模拟证实，由于强烈的空间n·π相互作用和受限的主链运动，主链中的平面π电子导致了红移发射。此外，设计的HBPSi-CBD与l-蛋氨酸偶联后可用作ROS清除剂。 HBPSi-Met 具有显着的 ROS 清除性能，清除能力为 77%。这项工作不仅进一步深入了解了非共轭超支化 AIE 聚合物的结构-性能关系，而且为治疗 ROS 相关疾病提供了一种有前途的 ROS 清除生物材料。