Single-crystal X-ray diffraction studies of pristine and γ-irradiated Ca₂[UO₂(O₂)₃]·9H₂O 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 Ca²⁺ is progressively replaced by two hydroxyl groups separated by 2.7 Å (with minor changes in the unit cell), whereas the peroxide groups bonded to Ca²⁺ cations are largely unaffected by irradiation prior to amorphization, which occurs by a dose of 3 MGy. The conversion of peroxide to hydroxyl occurs through interaction of neighboring lattice H₂O molecules and ionization of the peroxide O-O bond, which produces two hydroxyls, and allows isolation of the important monomer building block, UO₂(O₂)₂(OH)₂^4-, that is ubiquitous in uranyl capsule polyoxometalates. Steric crowding in the equatorial plane of the uranyl ion develops and promotes transformation to an amorphous phase. In contrast, γ-irradiation of solid Li₄[(UO₂)(O₂)₃]·10H₂O results in a solid-state transformation to a well-crystallized peroxide-free uranyl oxyhydrate containing sheets of equatorial edge and vertex-sharing uranyl pentagonal bipyramids with likely Li and H₂O in interlayer positions. The irradiation products of these two uranyl triperoxide monomers are compared via X-ray diffraction (single-crystal and powder) and Raman spectroscopy, with a focus on the influence of the Li⁺ and Ca²⁺ countercations. Highly hydratable and mobile Li⁺ yields to uranyl hydrolysis reactions, while Ca²⁺ provides lattice rigidity, allowing observation of the first steps of radiation-promoted transformation of uranyl triperoxide.

Nicholas A. Poole

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