Chen Hongming, Yang Xi, Ye Yuanji, Hong HongYang, Wei Qingsong, Zhu Yanan, Lin Mei-Jin
College of Materials Science and Engineering, Fuzhou University, Fuzhou, 350116, P.R. China.
College of Chemical Engineering, Fuzhou University, Fuzhou, 350116, P.R. China.
Angew Chem Int Ed Engl. 2025 Jul;64(27):e202506118. doi: 10.1002/anie.202506118. Epub 2025 May 8.
Lanthanide-based metal-organic framework (Ln-MOF) scintillators are promising for X-ray imaging owing to their structural tunability and high X-ray attenuation. However, achieving efficient triplet-sensitized scintillation remains challenging due to the inefficient energy transfer between organic ligand triplets and lanthanide centers, leading to weak radioluminescence and limited imaging resolution. Herein, we propose a dual-antenna ligand strategy by synergizing 4,4'-oxybis (benzoic acid) (Oba) and phenanthroline derivatives (1,10-phenanthroline = Phen; or Bathophenanthroline = Bphen) with Eu ions, constructing ultrabright Eu-O-Phen and Eu-O-Bphen scintillators. Notably, Eu-O-Bphen demonstrated a record relative light yield of 60331 ± 28 photons MeV, outperforming Eu-O-Phen by 71%. This superior scintillation performance originates from an 86.3 ± 0.19% photoluminescence quantum yield, attributed to enhanced ligand-to-metal energy transfer efficiency and the suppression of π-π stacking among organic chromophore ligands. Besides, the fabrication of flexible Eu-O-Bphen films achieves a spatial resolution of 37.0 lp mm in static imaging and enables real-time dynamic X-ray imaging at 60 fps (2 K). Additionally, it exhibited exceptional water stability, with negligible performance degradation in water for over 100 days, allowing clear underwater visualization of circuit boards under X-ray irradiation. It provides a promising strategy for developing high-performance water-stable scintillators via ligand engineering.
基于镧系元素的金属有机框架（Ln-MOF）闪烁体因其结构可调性和高X射线衰减性而在X射线成像方面具有广阔前景。然而，由于有机配体三线态与镧系元素中心之间的能量转移效率低下，实现高效的三线态敏化闪烁仍然具有挑战性，这导致辐射发光较弱且成像分辨率有限。在此，我们提出了一种双天线配体策略，通过将4,4'-氧双（苯甲酸）（Oba）和菲咯啉衍生物（1,10-菲咯啉 = Phen；或二氮杂菲 = Bphen）与铕离子协同作用，构建了超亮的Eu-O-Phen和Eu-O-Bphen闪烁体。值得注意的是，Eu-O-Bphen的相对光产额达到了创纪录的60331±28光子 MeV，比Eu-O-Phen高出71%。这种优异的闪烁性能源于86.3±0.19%的光致发光量子产率，这归因于配体到金属的能量转移效率提高以及有机发色团配体之间π-π堆积的抑制。此外，柔性Eu-O-Bphen薄膜的制备在静态成像中实现了37.0 lp mm的空间分辨率，并能够以60 fps（2K）进行实时动态X射线成像。此外,它还表现出出色的水稳定性，在水中超过100天性能降解可忽略不计，能够在X射线照射下清晰地对水下电路板进行可视化。它为通过配体工程开发高性能水稳定闪烁体提供了一种有前景的策略。
