Expanding the Crystal Chemistry of Actinyl Peroxides: μ-η2:η1 Peroxide Coordination in Trimers of U6+ Polyhedra

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Uranyl peroxides have been intensively studied recently because they form topologically complex structures including spherical clusters containing tens of uranyl polyhedra. In all uranyl peroxides reported to date, the coordination of U(6+) cations by peroxide is bidentate. The compound K(2)(Mg(H(2)O)(6))(4)[(UO(2))(3)(O(2))(8)].2H(2)O has been synthesized and characterized and contains a trimer of linked uranyl peroxide polyhedra. The central U(6+) cation is linked to two peroxide groups in a mu-eta(2):eta(1) configuration. Inclusion of this mode of linkage could dramatically increase the flexibility and topological complexity of uranyl peroxide nanoscale clusters.