title: Hierarchy of Pyrophosphate-Functionalized Uranyl Peroxide Nanocluster Synthesis.
abstract: Herein, we report a new salt of a pyrophosphate-functionalized uranyl peroxide nanocluster {U24Pp12} (1) exhibiting Ohmolecular symmetry both in the solid and solution. Study of the system yielding 1 across a wide range of pH by single-crystal X-ray diffraction, small-angle X-ray scattering, and a combination of traditional31P and diffusion-ordered spectroscopy (DOSY) NMR affords unprecedented insight into the amphoteric chemistry of this uranyl peroxide system. Key results include formation of a rare binary {U24}·{U24Pp12} (3) system observed under alkaline conditions, and evidence of acid-promoted decomposition of {U24Pp12} (1) followed by spatial rearrangement and condensation of {U4} building blocks into the {U32Pp16} (2) cluster. Furthermore,31P DOSY NMR measurements performed on saturated solutions containing crystalline {U32Pp16} show only trace amounts (∼2% relative abundance) of the intact form of this cluster, suggesting a complex interconversion of {U24Pp12}, {U32Pp16}, and {U4Pp4-x} ions.
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: Mateusz
authors.initials: M
authors.lastname: Dembowski
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Colla
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: Sarah
authors.initials: S
authors.lastname: Hickam
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: Anna F
authors.initials: AF
authors.lastname: Oliveri
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: Jennifer E S
authors.initials: JES
authors.lastname: Szymanowski
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: Allen G
authors.initials: AG
authors.lastname: Oliver
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: William H
authors.identifier: http://orcid.org/0000-0002-3275-6465
authors.initials: WH
authors.lastname: Casey
authors.affiliation: Department of Chemistry and Biochemistry and §Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Earth and Planetary Sciences and ∥Department of Chemistry, University of California , Davis, California 95616, United States.
authors.forename: Peter C
authors.identifier: http://orcid.org/0000-0002-2319-9628
authors.initials: PC
authors.lastname: Burns