High Uptake of ReO4− by a Radiation Resistant [Th48Ni6] Nanocage-Based Metal−Organic Framework

Assembled from [Th48Ni6] nanocages, the first transion‐metal (TM)‐Th metal‐organic framework (MOF, 1) has been synthesized and structurally characterized. 1 exhibits high solvent and acid/base stability, and resistance to 400 kGy β irradiation. Notably, 1 captures ReO4− (an analog of radioactive 99TcO4−, a key species in nuclear wastes) with a maximum capacity of 807 mg/g, falling among the largest values known to date. Furthermore, 1 can enrich methylene blue (MB) and can also serve as an effective and recyclable catalyst for CO2 fixation with epoxides; there is no significant loss of catalytic activity after 10 cycles. Theoretical studies with nucleus‐independent chemical shifts and natural bond orbital analysis reveal that the [Th6O8] clusters in 1 have a unique stable electronic structure with (d‐p)π aromaticity, partialy rationalising 1’s stability.