Wang Guangming, Chen Xuefeng, Li Xun, Zeng Ying, Zhang Kaka
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 People's Republic of China
Chem Sci. 2023 Jul 6;14(30):8180-8186. doi: 10.1039/d3sc01500a. eCollection 2023 Aug 2.
Manipulation of excited states and their dynamics represents a central topic in luminescence systems. We report an unexpected emergence of a high-performance organic afterglow in pyrylium induced photopolymerization systems, as well as the establishment of the mechanism landscape of the afterglow systems as a function of monomer types. In the case of methyl methacrylate, after pyrylium-catalyzed photopolymerization, the obtained materials exhibit a TADF-type organic afterglow with an afterglow efficiency of 70.4%. By using heavy-atom-containing methacrylate, the external heavy atom effect speeds up phosphorescence decay and switches on room-temperature phosphorescence in pyrylium-polymer systems. When 9-vinylcarbazole is used, the resultant materials display organic long persistent luminescence with hour-long durations and emission maxima around 650 nm. The intriguing mechanism landscape reflects the delicate balance of multiple photophysical processes in the pyrylium induced organic afterglow systems, which has been rarely explored in the reported studies.
激发态的调控及其动力学是发光系统的核心主题。我们报道了在吡喃鎓引发的光聚合体系中意外出现的高性能有机余辉，以及作为单体类型函数的余辉体系机理图景的建立。在甲基丙烯酸甲酯的情况下，经吡喃鎓催化光聚合后，所得材料呈现出TADF型有机余辉，余辉效率为70.4%。通过使用含重原子的甲基丙烯酸酯，外部重原子效应加速了磷光衰减，并开启了吡喃鎓聚合物体系中的室温磷光。当使用9-乙烯基咔唑时，所得材料显示出长达数小时的有机长余辉，发射最大值在650 nm左右。这种有趣的机理图景反映了吡喃鎓引发的有机余辉体系中多个光物理过程的微妙平衡，这在已报道的研究中很少被探索。
