A New Molybdenum Blue Structure Type: How Uranium Expands this Family of Polyoxometalates.

The assembly of molybdenum polyoxometalates (POMs) has afforded large discrete nanoclusters with varied degrees of reduction such as the ~20 % reduced molybdenum blues. While many heterometals have been incorporated into these clusters to afford new properties, uranium has yet to be reported. Here we report the first uranium containing molybdenum blue clusters and the unique properties exhibited by this incorporation.

Radiation-Induced Solid-State Transformations of Uranyl Peroxides.

Single-crystal X-ray diffraction studies of pristine and γ-irradiated Ca[UO(O)]·9HO reveal site-specific atomic-scale changes during the solid-state progression from a crystalline to X-ray amorphous state with increasing dose. Following γ-irradiation to 1, 1.5, and 2 MGy, the peroxide group not bonded to Ca is progressively replaced by two hydroxyl groups separated by 2.