Coupling Robust 222Rn Capture With Scintillation Readout in High-Entropy Lanthanide-Cluster Metal-Organic Framework Scintillators.

Efficient capture-coupled detection of hazardous 222Rn requires porous scintillators that integrate noble-gas affinity, structural robustness, and radioluminescent readout under practical operating conditions. Here, we report two fluoride-bridged, lanthanide-cluster MOF scintillators, Tb-LOF-100 and Tb-LOF-101, together with their high-entropy lanthanide-node analogues (Ln-LOF-100 and Ln-LOF-101), to elucidate how high-entropy node engineering regulates 222Rn capture and radiation-responsive performance. The high-entropy MOFs retain the crystalline phases and permanent porosity of their Tb-based parents, while exhibiting enhanced thermal, moisture, and γ-irradiation stability. In particular, Ln-LOF-101 delivers a static 222Rn uptake capacity of 46.1 Bq g-1 and a breakthrough adsorption coefficient of 10.9 Lg-1 for 222Rn, ranking among the best-performing adsorbents reported for Rn capture under ambient conditions. Notably, Ln-LOF-101 exhibits an unusual moisture-enhanced noble-gas adsorption behavior. Xe-loaded single-crystal diffraction of Tb-LOF-101, combined with molecular simulations for Rn, identifies four preferential Rn binding sites concentrated around the metal node. Compared with the parent Tb-MOFs, the high-entropy MOFs show improved radioluminescence retention under repeated X-ray irradiation, and their radioluminescence response toward 222Rn confirms their detection capability. Despite the trade-off between gas adsorption capability and scintillation efficiency, our work establishes high-entropy lanthanide-node engineering as a designable strategy for integrating radioactive-gas capture, radiation tolerance, and scintillation readout within porous MOF platforms.