Sandwich-Type Uranyl Phosphate-Polyoxometalate Cluster Exhibiting Strong Luminescence

A pure inorganic uranyl phosphate-polyoxometalate of Na₁₇{Na@[(SbW₉O₃₃)₂(UO₂)₆(PO₃OH)₆]}·xH₂O (abbreviated as Na@UP, with x ≈ 46) featuring a sandwich-type structure was prepared using Keggin-type trilacunary [α-B-SbW₉O₃₃]^9- units as building blocks, which were formed in situ by SbCl₃ and Na₂WO₄·2H₂O. Crystal structural analysis showed that six UO₂²⁺ cations and six PO₃OH^2- anions generated a wheel-like cluster unit with a Na⁺ center ([Na@(UO₂)₆(PO₃OH)₆]⁺) that is stabilized by two [α-B-SbW₉O₃₃]^9- units. Na@UP displayed a solid-state photoluminescence quantum yield of 33% at 300 K. The temperature-dependent fluorescence emission spectra showed that Na@UP has temperature-sensitive fluorescence in which its emission intensity decreased by 77% as the temperature increased from 200 to 300 K. These results suggest that such uranyl phosphate-polyoxometalate clusters could serve as potential temperature-sensitive molecular materials.