School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China.
Small. 2023 May;19(18):e2207403. doi: 10.1002/smll.202207403. Epub 2023 Feb 12.
It is still very challenging to obtain colorful and long-afterglow room-temperature phosphorescent (RTP) materials from pure organic polymers. Herein, it is found that chitosan (CS), a natural polymer, not only has its own RTP, but also reacts with different phosphorescent molecules to obtain a multicolor, long-afterglow RTP material. CS can emit RTP with a lifetime of 48 ms. In addition, CS is rich in amino groups, and grafting different phosphorescent molecules onto CS by an amidation reaction can modulate it to emit different colors of phosphorescence and obtain a series of colorful CS derivatives. The obtained polymer films also have ultra-long RTP due to the good film-forming ability. In addition, one of the CS derivatives selected with α-cyclodextrin is used to construct RTP materials with lifetimes of up to seconds. The host-guest interactions are used to suppress nonradiative relaxation and build crystalline domains, thus synergistically enhancing the RTP. Interestingly, the RTP properties of the CS derivative films are extremely sensitive to water and heat stimuli, because water broke the hydrogen bonds between adjacent CS molecules and thus altered the rigid environment in the material. Finally, they can be used as a stimuli-responsive ink and for monitoring environmental humidity.
从纯有机聚合物中获得彩色和长余辉室温磷光(RTP)材料仍然极具挑战性。在此,人们发现天然聚合物壳聚糖(CS)不仅具有自身的 RTP,还可以与不同的磷光分子反应,从而获得多色、长余辉 RTP 材料。CS 可以发射寿命为 48ms 的 RTP。此外,CS 富含氨基,通过酰胺化反应将不同的磷光分子接枝到 CS 上,可以调节其发射不同颜色的磷光,并获得一系列彩色 CS 衍生物。由于具有良好的成膜能力,所得聚合物薄膜也具有超长的 RTP。此外,选择具有 α-环糊精的一种 CS 衍生物来构建寿命长达数秒的 RTP 材料。主客体相互作用可抑制非辐射弛豫并构建结晶域,从而协同增强 RTP。有趣的是,CS 衍生物薄膜的 RTP 性质对水热刺激极为敏感,因为水破坏了相邻 CS 分子之间的氢键,从而改变了材料中的刚性环境。最后,它们可用作对环境湿度具有响应性的墨水和用于监测环境湿度。