Ionic-Liquid-Based Synthesis of U24 Uranyl Peroxide Cage Clusters with Encapsulated Hexanuclear Lanthanide Oxide/Hydroxide Clusters

Cale B. Gaster; Daniel E. Felton; Teagan F.M. Sweet; Brodie Barth; Allen G. Oliver; Arianna Latuda; Jada Rogers; Peter C. Burns

doi:10.1021/acs.inorgchem.5c00161

Ionic-Liquid-Based Synthesis of U₂₄ Uranyl Peroxide Cage Clusters with Encapsulated Hexanuclear Lanthanide Oxide/Hydroxide Clusters

Cale B. Gaster, Daniel E. Felton, Teagan F.M. Sweet, Brodie Barth, Allen G. Oliver, Arianna Latuda, Jada Rogers, Peter C. Burns

Materials & Chemistry Group

Research output: Contribution to journal › Article › peer-review

Abstract

Six lanthanide-containing (Pr-Tb, excluding Pm) uranyl peroxide cage clusters (UPCs) formed following the dissolution of studtite, [(UO₂)(O₂)(H₂O)₂](H₂O)₂, and lanthanide nitrates in the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate (EMIm-DEP). Crystals of the compounds were isolated and characterized using single crystal X-ray diffraction, Raman and infrared spectroscopy, and scanning electron microscopy with energy-dispersive X-ray spectroscopy. The six structures are composed of U₂₄, [(UO₂)₂₄(O₂)₂₄(OH)₂₄]^24-, cage clusters with the sodalite topology encapsulating [Ln₆O(OH)₈]⁸⁺ hexanuclear units. The crystal packing of the cage clusters produces a highly porous crystal structure and nonlocalized EMIm-DEP ions reside in pores within the crystal structure, providing charge-balance to the anionic cage clusters. Adjacent U₂₄ cages are directly linked through hydrogen bonds donated by hydroxy groups of one cluster and accepted by uranyl ion oxygen atoms of another. The typical UPC synthesis involves decomposition of studtite in alkaline aqueous conditions, making the formation of Ln-containing UPCs impractical owing to the precipitation of insoluble lanthanide compounds under such conditions. This is the first report of studtite dissolving in an ionic liquid and subsequently forming UPCs, as well as the first report of the formation of U₂₄ containing lanthanide cations.

Original language	English
Pages (from-to)	8082-8088
Number of pages	7
Journal	Inorganic Chemistry
Volume	64
Issue number	16
DOIs	https://doi.org/10.1021/acs.inorgchem.5c00161
State	Published - Apr 28 2025

Funding

This research was funded by the University of Notre Dame. T.F.M.S. was supported by a Nuclear Energy Graduate Fellowship through the DOE Office of Nuclear Energy (NE) University Nuclear Leadership Program (UNLP).

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10.1021/acs.inorgchem.5c00161

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title = "Ionic-Liquid-Based Synthesis of U24 Uranyl Peroxide Cage Clusters with Encapsulated Hexanuclear Lanthanide Oxide/Hydroxide Clusters",

abstract = "Six lanthanide-containing (Pr-Tb, excluding Pm) uranyl peroxide cage clusters (UPCs) formed following the dissolution of studtite, [(UO2)(O2)(H2O)2](H2O)2, and lanthanide nitrates in the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate (EMIm-DEP). Crystals of the compounds were isolated and characterized using single crystal X-ray diffraction, Raman and infrared spectroscopy, and scanning electron microscopy with energy-dispersive X-ray spectroscopy. The six structures are composed of U24, [(UO2)24(O2)24(OH)24]24-, cage clusters with the sodalite topology encapsulating [Ln6O(OH)8]8+ hexanuclear units. The crystal packing of the cage clusters produces a highly porous crystal structure and nonlocalized EMIm-DEP ions reside in pores within the crystal structure, providing charge-balance to the anionic cage clusters. Adjacent U24 cages are directly linked through hydrogen bonds donated by hydroxy groups of one cluster and accepted by uranyl ion oxygen atoms of another. The typical UPC synthesis involves decomposition of studtite in alkaline aqueous conditions, making the formation of Ln-containing UPCs impractical owing to the precipitation of insoluble lanthanide compounds under such conditions. This is the first report of studtite dissolving in an ionic liquid and subsequently forming UPCs, as well as the first report of the formation of U24 containing lanthanide cations.",

author = "Gaster, {Cale B.} and Felton, {Daniel E.} and Sweet, {Teagan F.M.} and Brodie Barth and Oliver, {Allen G.} and Arianna Latuda and Jada Rogers and Burns, {Peter C.}",

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doi = "10.1021/acs.inorgchem.5c00161",

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T1 - Ionic-Liquid-Based Synthesis of U24 Uranyl Peroxide Cage Clusters with Encapsulated Hexanuclear Lanthanide Oxide/Hydroxide Clusters

AU - Gaster, Cale B.

AU - Felton, Daniel E.

AU - Sweet, Teagan F.M.

AU - Barth, Brodie

AU - Oliver, Allen G.

AU - Latuda, Arianna

AU - Rogers, Jada

AU - Burns, Peter C.

PY - 2025/4/28

Y1 - 2025/4/28

N2 - Six lanthanide-containing (Pr-Tb, excluding Pm) uranyl peroxide cage clusters (UPCs) formed following the dissolution of studtite, [(UO2)(O2)(H2O)2](H2O)2, and lanthanide nitrates in the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate (EMIm-DEP). Crystals of the compounds were isolated and characterized using single crystal X-ray diffraction, Raman and infrared spectroscopy, and scanning electron microscopy with energy-dispersive X-ray spectroscopy. The six structures are composed of U24, [(UO2)24(O2)24(OH)24]24-, cage clusters with the sodalite topology encapsulating [Ln6O(OH)8]8+ hexanuclear units. The crystal packing of the cage clusters produces a highly porous crystal structure and nonlocalized EMIm-DEP ions reside in pores within the crystal structure, providing charge-balance to the anionic cage clusters. Adjacent U24 cages are directly linked through hydrogen bonds donated by hydroxy groups of one cluster and accepted by uranyl ion oxygen atoms of another. The typical UPC synthesis involves decomposition of studtite in alkaline aqueous conditions, making the formation of Ln-containing UPCs impractical owing to the precipitation of insoluble lanthanide compounds under such conditions. This is the first report of studtite dissolving in an ionic liquid and subsequently forming UPCs, as well as the first report of the formation of U24 containing lanthanide cations.

AB - Six lanthanide-containing (Pr-Tb, excluding Pm) uranyl peroxide cage clusters (UPCs) formed following the dissolution of studtite, [(UO2)(O2)(H2O)2](H2O)2, and lanthanide nitrates in the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate (EMIm-DEP). Crystals of the compounds were isolated and characterized using single crystal X-ray diffraction, Raman and infrared spectroscopy, and scanning electron microscopy with energy-dispersive X-ray spectroscopy. The six structures are composed of U24, [(UO2)24(O2)24(OH)24]24-, cage clusters with the sodalite topology encapsulating [Ln6O(OH)8]8+ hexanuclear units. The crystal packing of the cage clusters produces a highly porous crystal structure and nonlocalized EMIm-DEP ions reside in pores within the crystal structure, providing charge-balance to the anionic cage clusters. Adjacent U24 cages are directly linked through hydrogen bonds donated by hydroxy groups of one cluster and accepted by uranyl ion oxygen atoms of another. The typical UPC synthesis involves decomposition of studtite in alkaline aqueous conditions, making the formation of Ln-containing UPCs impractical owing to the precipitation of insoluble lanthanide compounds under such conditions. This is the first report of studtite dissolving in an ionic liquid and subsequently forming UPCs, as well as the first report of the formation of U24 containing lanthanide cations.

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ER -

Ionic-Liquid-Based Synthesis of U₂₄ Uranyl Peroxide Cage Clusters with Encapsulated Hexanuclear Lanthanide Oxide/Hydroxide Clusters

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