Flux crystal growth, structure, magnetic and optical properties of a family of alkali uranium(IV) phosphates

Usman, Mohammad; Morrison, Gregory; Klepov, Vladislav V.; Smith, Mark D.; Loye, Hans‐Conrad zur

doi:10.1016/j.jssc.2018.10.033

Cited by 7 publications

(7 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Similar to U IV oxides, U 6 and U 38 exhibit transition of the 5f 2 electrons from unpaired to paired with cooling. Typically, high coordination U IV compounds (CN = 8) exhibit Curie−Weiss behavior, 62 whereas lower coordination numbers (CN = 6) lead to non-Curie-like behavior due to strong crystalline electric field effects. 63 Recently, a Mn-U IV fluoride was described with magnetic coupling between the 3d and 5f electrons, 64 piquing interest in magnetic properties of U IV -TM/Ln oxo clusters and oxides.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations

et al. 2020

Self Cite

View full text Add to dashboard Cite

Superatoms are nanometer-sized molecules or particles that form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in lattices of quantum dots, p-block clusters, and fullerenes. Here, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters: acidity and the lanthanide or transition-metal countercation. In acid, larger LnIII (Ln = La–Ho) link hexamer (U6) oxoclusters into body-centered cubic frameworks, while smaller LnIII (Ln = Er–Lu and Y) promote linking of 14 U6 clusters into hollow superclusters (U84 superatoms). U84 assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations and U6 clusters. Divalent transition metals (TM = MnII and ZnII) charge-balance and promote the fusion of 10 U6 and 10 U monomers into a wheel-shaped cluster (U70). Dissolution of U70 in organic media reveals (by small-angle X-ray scattering) that differing supramolecular assemblies are accessed, controlled by TMII-linking of U70 clusters. Magnetic measurements of these assemblies reveal Curie–Weiss behavior at high temperatures, without pairing of the 5f2-electrons down to 2 K.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…Similar to U IV -oxides, U6 and U38 exhibit transition of the 5f 2 electrons from unpaired to paired with cooling. Typically, high coordination U IV -compounds (CN = 8) exhibit Curie-Weiss behavior 49 whereas lower coordination numbers (CN = 6) lead to non-Curie-like behavior due to strong crystalline electric field effects. 50 Recently, a Mn-U IV fluoride was described with magnetic coupling between the 3d and 5f electrons, 51 piquing interest in magnetic properties of U IV -TM/Ln oxo-clusters and oxides.…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Assembly of U(IV) Clusters and Superatoms

Colliard¹,

Morrison²,

Loye³

et al. 2020

Preprint

Self Cite

View full text Add to dashboard Cite

Superatoms are nanometer-sized molecules or particles that can form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in superlattices of quantum-dots, p-block clusters, and fullerenes. Here, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters; acidity and the countercation. In acid, larger LnIII (Ln=La-Ho) link hexamer (U6) oxoclusters into body-centered cubic frameworks, while smaller LnIII (Ln=Er-Lu &Y) promote linking of fourteen U6-clusters into hollow superclusters (U84 superatoms). U84 assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations, and U6-clusters. Divalent transition metals (TM=MnII and ZnII), with no added acid, charge-balance and promote the fusion of 10 U6 and 10 U-monomers into a wheel–shaped cluster (U70). Dissolution of U70 in organic media reveals (by small-angle Xray scattering) that differing supramolecular assemblies are accessed, controlled by TM-linking of U70-clusters.

show abstract

“…In alkali metal-actinide (IV) -phosphates, system structural, thermal, magnetic and optical properties of several quaternary compounds have been well reported. [23][24][25][26][27][28][29][30] Synthesis and properties of alkali metal uranium phosphates of the formula AM I U IV 2 (PO 4 ) 3 , have been studied by Usman et al [23] Temperature dependent transition in AM I M 2 IV (PO 4 ) 3 ; (M IV = U/ Np/Pu and AM I = Na/K/Rb) type of compounds and their structural studies have been carried out by Volkov et al [24] Structural information on complete substitution of uranium by thorium in K(Th 1-x U x ) 2 (PO 4 ) 3 using single crystal technique have been provided by Guesdon et al [25] Crystal structure of potassium thorium triphosphate, KThP 3 O 10 has been determined by Toros et al [26] Structural and thermal study of M I Th 2 (PO 4 ) 3 type phosphates has been carried out by Krishnan et al [27] Yu et al have revealed the synthesis and structural studies of number of iso structural alkali metal thorium phosphates and arsenates. [28,29] Temperature dependent struc-tural study, phase transition and thermal expansion behavior in K 2 Th(PO 4 ) 2 has been carried out by Bevara et al [30] whereas crystal structure of Na 6 [Th(PO 4 )(P 2 O 7 )] 2 has been determined by Prodic et al [31] As compared to structural data, limited data is available on thermal properties of alkali metal thorium phosphates.…”

Section: Introductionmentioning

confidence: 99%

“…As coordination chemistry of thorium is similar to those of U 4+ and transuranic Np 4+ , Pu 4+ elements, thorium compounds are extensively studied as surrogate materials for tetravalent U, Pu and Np elements. In alkali metal‐actinide (IV) ‐phosphates, system structural, thermal, magnetic and optical properties of several quaternary compounds have been well reported [23–30] . Synthesis and properties of alkali metal uranium phosphates of the formula AM I U IV 2 (PO 4 ) 3 , have been studied by Usman et al [23] .…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Thermal Properties of Alkali Metal Thorium Phosphates and Their Application for the Sorption of Uranyl Ion from Acidic Medium

et al. 2023

View full text Add to dashboard Cite

Thermo physical properties of potassium, rubidium and cesium thorium phosphate compounds were investigated. All compounds were synthesized by conventional solid state method. Formation of orthorhombic AMThP3O10, tetragonal AM2Th(PO4)2 and monoclinic AMTh2(PO4)3; [AM=K, Rb and Cs] was confirmed using Powder X‐ray diffraction (XRD) technique. Structural study of CsThP3O10 was carried out for the first time from Rietveld refinement of XRD data. Thermal stability of all compounds was established using Thermogravimetric analysis (TGA) technique. When heated at 1673 K for 30 h in air, all the compounds decompose to ThO2. High temperature X‐ray diffraction (HT‐XRD) data of the compounds, synthesized during present study, were collected in an inert atmosphere from ambient to 973 K and their thermal expansion coefficients were calculated. These compounds show positive thermal expansion up to 973 K. Molar heat capacities for all phosphates were measured between 300–863 K using Differential Scanning Calorimeter. Alkali metal thorium phosphates, AMThP3O10 and AMTh2(PO4)3, showed efficient uptake of uranyl ion from aqueous acidic medium predominantly following Langmuir isotherm and Webber Morris intra particle diffusion kinetics.

show abstract

Flux crystal growth, structure, magnetic and optical properties of a family of alkali uranium(IV) phosphates

Cited by 7 publications

References 43 publications

Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations

Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations

Supramolecular Assembly of U(IV) Clusters and Superatoms

Investigation of the Thermal Properties of Alkali Metal Thorium Phosphates and Their Application for the Sorption of Uranyl Ion from Acidic Medium

Contact Info

Product

Resources

About