title: Sulfate-Centered Sodium-Icosahedron-Templated Uranyl Peroxide Phosphate Cages with Uranyl Bridged by μ-η1:η2Peroxide.
abstract: Two novel hybrid uranyl peroxide phosphate cage clusters, designated U20P6and U20P12, contain peroxide bridges between uranyl in an unusual μ-η1:η2configuration, as well as the common μ-η2:η2configuration. These appear to be the only high-nuclearity metal peroxide complexes containing μ-η1:η2peroxide bridges, and they are unique among uranyl peroxide cages. Both clusters contain 20 uranyl polyhedra, and U20P6and U20P12contain 6 and 12 phosphate tetrahedra, respectively. The 20 uranyl polyhedra in both cages are arranged on the vertices of distorted topological dodecahedrons (20 vertex fullerenes). Each cage is completed by phosphate tetrahedra and is templated by a sulfate-centered Na12cluster with the Na cations defining a regular convex isocahedron. Whereas μ-η2:η2peroxides are essential features of uranyl peroxide cages, where they form equatorial edges of uranyl hexagonal bipyramids, the μ-η1:η2peroxide groups in U20P6and U20P12are associated with strong distortions of the uranyl polyhedra. Formation of U20P6and U20P12is a further demonstration of the pliable nature of uranyl polyhedra, which contributes to the tremendous topological variability of uranyl compounds. Despite the unusual structure and highly distorted polyhedral geometries of U20P6, small-angle X-ray scattering and Raman spectra suggest its stability in the aqueous solution and solid state.
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences and ‡Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Jie
authors.initials: J
authors.lastname: Qiu
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences and ‡Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Tyler L
authors.identifier: http://orcid.org/0000-0001-6572-9722
authors.initials: TL
authors.lastname: Spano
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences and ‡Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Mateusz
authors.initials: M
authors.lastname: Dembowski
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences and ‡Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Alex M
authors.initials: AM
authors.lastname: Kokot
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences and ‡Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Jennifer E S
authors.initials: JE
authors.lastname: Szymanowski
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences and ‡Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Peter C
authors.identifier: http://orcid.org/0000-0002-2319-9628
authors.initials: PC
authors.lastname: Burns