Wang Zheng, Pan Jun-Jie, Chen Xin-Qi, Li Meng-Yang, Wang Shi-Cheng
Key Laboratory of Chemical Additives for China National Light Industry, College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi'an, 710021, China.
School of Physics, Xidian University, Xi'an, 710071, China.
Chemistry. 2024 Dec 5;30(68):e202402806. doi: 10.1002/chem.202402806. Epub 2024 Oct 16.
Tunable luminescence-assisted information storage and encryption holds increasing significance in today's society. A promising approach to incorporating the benefits of both organic long persistent luminescent (LPL) materials and rare-earth (RE) luminescence lies in utilizing organic host materials to sensitize RE luminescence, as well as employing Förster resonance energy transfer from hydrogen-bonded organic framework (HOF) phosphorescence to RE compound luminescence. This work introduces a one-pot, in situ pyrolytic condensation method, achieved through high-temperature melting calcination, to synthesize lanthanide ion-doped HOF materials. This method circumvents the drawback of molecular triplet energy annihilation, enabling the creation of organic LPL materials with RE characteristics. The HOF material serves as the host, exhibiting blue phosphorescence and cyan LPL. By fine-tuning the doping amount, the composite material U-Tb-100 achieves green LPL with a luminescent quantum yield of 56.4 %, and an LPL duration of approximately 2-3 s, demonstrating tunable persistence. Single-crystal X-ray diffraction, spectral analysis, and theoretical calculation unveil that U-Tb-100 exhibits exceptional quantum yield and long-lived luminescence primarily due to the efficient sensitization of U monomer to RE ions and the PRET process between U and RE complexes. This ingenious strategy not only expands the repertoire of HOF materials but also facilitates the design of multifunctional LPL materials.
可调谐发光辅助信息存储和加密在当今社会具有越来越重要的意义。一种结合有机长余辉发光(LPL)材料和稀土(RE)发光优点的有前途的方法是利用有机主体材料来敏化RE发光,以及采用从氢键有机框架(HOF)磷光到RE化合物发光的Förster共振能量转移。这项工作介绍了一种通过高温熔融煅烧实现的一锅原位热解缩合方法,用于合成镧系离子掺杂的HOF材料。该方法规避了分子三重态能量湮灭的缺点,能够制备具有RE特性的有机LPL材料。HOF材料作为主体,呈现蓝色磷光和青色LPL。通过微调掺杂量,复合材料U-Tb-100实现了绿色LPL,发光量子产率为56.4%,LPL持续时间约为2-3秒,展示了可调谐的持久性。单晶X射线衍射、光谱分析和理论计算表明,U-Tb-100表现出优异的量子产率和长寿命发光,主要是由于U单体对RE离子的有效敏化以及U与RE配合物之间的PRET过程。这种巧妙的策略不仅扩展了HOF材料的种类,还促进了多功能LPL材料的设计。