南京大学揭克诚团队报道了海绵状大环晶体的正向和反向气相荧光。相关研究成果于2025年1月23日发表在国际知名学术期刊《德国应用化学》。

通过固态分子运动实现动态多色发光对于推进有机固态发光材料的应用具有重要意义。

该文中，研究人员报告了具有独特正向和反向荧光变色行为的大环晶体，这是通过可逆的胺蒸气吸收和胺“挤压”诱导的客体释放来实现的。当脂肪胺穿透无客体的大环晶体形成主客体络合物晶体时，会发生前向荧光变色。通过在晶体内进行竞争性客体置换，将负载胺的晶体暴露于另一种胺蒸气中，可以可逆地切换这些荧光特性。

值得注意的是，通过将负载胺的晶体暴露于α-甲基苄胺（MBA）来实现逆蒸发荧光变色。机制研究表明，MBA分子不会穿透晶体，而是“挤压”晶体以释放负载的胺，使负载胺的晶体回到无客体相。所展示的正向和反向荧光变色已经成功集成到一个高度安全的五层信息加密系统中。

附：英文原文

Title: Forward? and Retro?Vapofluorochromism of Sponge?Like Macrocycle Crystals

Author: Jingwei Huang, Haohui Feng, Linnan Zhang, Kecheng Jie

Issue&Volume: 2025-01-23

Abstract: Achieving dynamic multicolor emission through solid-state molecular motion is of significant importance for advancing applications in organic solid-state luminescent materials. Herein, we report macrocycle crystals with unique forward and retrovapofluorochromic behavior, which is realized by reversible amine vapor uptake and amine“squeeze” induced guest release. The forwardvapofluorochromism occurs when aliphatic amines penetrate guest-free macrocycle crystals to form hostguest complex crystals. These fluorescent properties can be reversibly toggled by exposing the amineloaded crystals to another amine vapor through competitive guest replacement inside the crystals. Notably, retrovapofluorochromism is achieved by exposing amineloaded crystals to αmethylbenzylamine (MBA). Mechanistic studies show that MBA molecules do not penetrate the crystal, but rather “squeeze” the crystals to release loaded amines, driving the amineloaded crystals back to the guest-free phase. The demonstrated forward and retrovapofluorochromism has already been successfully integrated into a highly secure fivelayer information encryption system.

DOI: 10.1002/anie.202500022

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202500022