Hu Danning, Mao Liucheng, Wang Mengshi, Huang Hongye, Hu Renjian, Ma Haijun, Yuan Jinying, Wei Yen
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China.
ACS Appl Mater Interfaces. 2022 Jan 19;14(2):3485-3495. doi: 10.1021/acsami.1c20758. Epub 2022 Jan 7.
The dynamic reversible Diels-Alder (DA) reactions play essential roles in both academic and applied fields. Currently, in situ visualization and direct monitoring of the formation and cleavage of covalent bonds in DA reactions are hampered by finite compatibility and expensive precise instruments, especially limited in solid reactions. We herein report a fluorescence system capable of in situ visualization by naked eyes and monitoring DA/retro-DA reactions. With the fluorescence quenching effect, the synthesized TPEMI could work as an innovative self-indicator for both DA termination and retro-DA occurrence. The fluorescence increases during DA reactions, and the mechanism is investigated to establish qualitative and quantitative relations. Besides rapid screening of reaction conditions and monitoring of DA exchange processes, the TPEMI fluorescence system can visualize heterogeneous and solid-state reactions with the AIE character. The TPEMI platform is expected to offer novel insights into reversible DA processes and dynamic covalent chemistry.
动态可逆的狄尔斯-阿尔德（DA）反应在学术和应用领域都发挥着重要作用。目前，DA反应中共价键形成和断裂的原位可视化及直接监测受到有限的兼容性和昂贵精密仪器的阻碍，尤其是在固相反应中受到限制。我们在此报告了一种能够通过肉眼进行原位可视化并监测DA/逆DA反应的荧光系统。基于荧光猝灭效应，合成的TPEMI可作为DA终止和逆DA发生的创新型自指示剂。DA反应过程中荧光增强，并对其机理进行了研究以建立定性和定量关系。除了快速筛选反应条件和监测DA交换过程外，TPEMI荧光系统还能通过聚集诱导发光（AIE）特性实现非均相和固态反应的可视化。TPEMI平台有望为可逆DA过程和动态共价化学提供新的见解。
