近日，中国科学院福建物质结构研究所尤磊团队研究了用于控制动态C-N键的全可见光偶氮苯光开关。相关论文于2025年4月16日发表在《中国化学》杂志上。

可见光驱动的光开关正受到广泛关注，但利用其光触发的结构变化来调节动态键合、组装和材料具有挑战性。在此，我们将醛环链互变异构体的可逆共价位点引入所有可见光偶氮苯中，为仲胺的动态C-N键的光控形成/交换提供了一个多功能平台。环链平衡的运动是通过操纵E/Z构型异构体的分子内多重氢键来实现的。

这种结构调节进一步实现了由仲胺形成和交换环半氨基醚的光控制动力学，仲胺表现出与E/Z异构体的动力学速率逆转。E/Z构型异构体参与偶氮连接羧酸盐与铵盐的多个氢键的能力不同是造成这种差异的原因。此外，偶氮苯在不同溶液中的光开关性能很容易通过与胺的动态共价反应来调节。可见光的动态反应性控制和相关的机理基础增加了光开关动态共价化学的集合，并将为后续的生物和材料应用奠定基础。

附：英文原文

Title: All-Visible-Light Azobenzene Photoswitches for Controlling Dynamic C—N Bonds†

Author: Yuanxue You, Ye Yang, Youming Lv, Hebo Ye, Hanwei Lu, Yichao Zeng, Lei You

Issue&Volume: 2025-04-16

Abstract: The visible light-driven photoswitches are attracting widespread attention, but it is challenging to leverage their phototriggered structural changes to regulate dynamic bonds, assemblies, and materials. Herein, we incorporated reversible covalent sites of aldehyde ring-chain tautomers into all-visible-light azobenzenes toward a versatile platform for light-controlled formation/exchange of dynamic C—N bonds from secondary amines. The movement of ring-chain equilibrium was attained via manipulating intramolecular multiple hydrogen bonding from E/Z configurational isomers. Such structural regulation further enabled photocontrolled kinetics for the formation and exchange reactions of cyclic hemiaminal ethers from secondary amines exhibiting kinetic rate reversal from E/Z isomers. The varied capability of E/Z configurational isomers in engaging in multiple hydrogen bonds of azo attached carboxylate with ammonium salt accounts for the difference. Moreover, the photoswitching performance of azobenzenes in different solutions was readily regulated by dynamic covalent reactions with amines. The dynamic reactivity control with visible light and associated mechanistic foundation add into the collection of photoswitchable dynamic covalent chemistry and would lay the foundation for subsequent biological and material applications.

DOI: 10.1002/cjoc.70027

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.70027