Further Insight into Uranium and Thorium Metaphosphate Chemistry and the Effect of Nd<sup>3+</sup> Incorporation into Uranium(IV) Metaphosphate

Yu, Na; Klepov, Vladislav V.; Neumeier, Stefan; Depmeier, Wulf; Bosbach, Dirk; Сулейманов, Е. В.; Alekseev, Evgeny V.

doi:10.1002/ejic.201403098

Cited by 12 publications

(6 citation statements)

References 33 publications

(53 reference statements)

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“…In contrast, the unbranched silicate chains in K 2 (UO 2 )Si 2 O 6 are built only from tertiary tetrahedra with the same Si/O oxygen ratio with that observed in K 14 (UO 2 ) 3 Si 10 O 30 . To date, all known single chain uranyl silicates have a 1:3 ratio which is identical to that observed in uranyl polyphosphates U(PO 3 ) 4 with achter single phosphate chains and K[(UO 2 )(P 3 O 9 )] with zwölf (12) chains.…”

Section: Resultssupporting

confidence: 59%

Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Kegler

Klepov

et al. 2018

Inorg. Chem.

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Two uranium and two thorium silicates were obtained using high temperature mixed fluxes methods. K(UO)SiO crystallizes in the P2/ c space group and contains open-branched sechser (six) single silicate chains, whereas K(UO)SiO crystallizes in the C2/ c space group and is built of unbranched achter (eight) silicate chains. The crystals of K(UO)SiO and K(UO)SiO are related by increasing U/Si molar ratios, and both structures contain the same secondary building units (SBUs), [USi] heptamers. The triangle diagram for all known A-UO-SiO phases demonstrates the high polymerization level of silicate groups in the system, which was compared with the family of A-UO-BO/BO compounds. For both thorium silicates, the transformation of KThSiO to KThSiO was found to be a factor of the reaction time. KThSiO crystallizes in the C2/ c space group and belongs to the NaSiSiO structure type. Its 3D framework consists of diorthosilicate SiO group and ThO octahedra. Noncentrosymmetric KThSiO crystallizes in the hexagonal P6 space group and adopts mineral wadeite-type structure based upon triorthosilicate SiO rings and ThO octahedra. The coordination environment of thorium for all existing oxo-anion compounds including B, Si/Ge, P/As, Cr/Mo/W, and S/Se/Te are summarized and analyzed. Additionally, spectroscopic properties of all novel materials have been studied.

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Section: Resultssupporting

confidence: 59%

Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Kegler

Klepov

et al. 2018

Inorg. Chem.

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“…Oxyphosphate ligands have been studied extensively and are known to exhibit various oxidation states, rich structural diversity, and different structural units ranging from isolated P(V)O 4 3– groups to infinite (P(V)O 3 – ) ∞ chains. − In contrast, there are only a few thiophosphate ligands reported so far, i.e., thiophosphate, P(V)S 4 3– , − thiopyrophosphate, P(V) 2 S 7 4– , ,, hexathiometadiphosphate, P(V) 2 S 6 2– , − and hexathiohypophosphate, P(IV) 2 S 6 4– . ,− The latter, P(IV) 2 S 6 4– , contains phosphorus in the +4 oxidation state and demonstrates a unique stability in aqueous solutions. The former three are highly moisture-sensitive, but can be stabilized in the crystal lattice for extended periods of time. , The majority of known thiophosphates are composed of either the simplest thiosphosphate unit, P(V)S 4 3– , or hexathiohypophosphite, P(IV) 2 S 6 4– anions.…”

Section: Introductionmentioning

confidence: 99%

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

et al. 2019

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To determine the influence of the lanthanide size on the structures and properties of thiophosphates, a thiophosphate series containing different lanthanides was synthesized via high temperature flux crystal growth and their structures and physical properties analyzed and compared. Layered thiohypophosphates NaLnP 2 S 6 (Ln = La, Ce, Pr) and thiopyrophosphates CsLnP 2 S 7 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Y) were grown out of an iodide flux using consistent reaction conditions across both series. Under the mildly reducing iodide flux reaction conditions, a rather rare example of phosphorus reduction from the +5 to the +4 oxidation state was observed. Both resultant structure types are based on lanthanide thiophosphate sheets with the alkali cations located between them. Magnetic susceptibility measurements were conducted and revealed Curie−Weiss behavior of the samples, with a Van Vleck contribution in the CsSmP 2 S 7 sample. UV−vis data was found to be in good agreement with the literature, indicating little influence of the sulfide environment on the localized 4f orbitals.

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“…These tetrahedra are connected together creating achter (eight) single germanate chains (Figure c). Although a great number of diverse oxo-anion chains have been found in uranyl silicate and phosphate systems, − less reports of compounds with single germanate chains were published until now. , The Ge–O–Ge angles in the single chain vary from 125.7(2)° to 145.0(7)° in the structure of the novel β-Cs 2 (UO 2 )Ge 2 O 6 . The remaining oxygen atoms of the infinite chain bond UO 6 polyhedra to produce the 3D structures with eight-membered rings.…”

Section: Resultsmentioning

confidence: 99%

Formation of Open Framework Uranium Germanates: The Influence of Mixed Molten Flux and Charge Density Dependence in U-Silicate and U-Germanate Families

Langer

Kegler

et al. 2018

Inorg. Chem.

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Seven novel open-framework uranyl germanates, K(UO)GeO, K(UO)GeO, α-Cs(UO)GeO, β-Cs(UO)GeO, Cs(UO)GeO, and A(UO)(GeO) (A = [NaKCl], [NaCsCl]), were grown from different mixed molten fluxes. The three-dimensional (3D) structure of K(UO)GeO with 8-ring channels can be built upon [UGe] pentamer secondary building units (SBUs). The 3D framework of K(UO)GeO with trapezoid (GeO) clusters consists of two types of [UGe] pentamers. The 3D framework of α-Cs(UO)GeO with 10-ring channels, crystallizing in the P2/ n space group, is constructed by [UGe] pentamers. The structure of β-Cs(UO)GeO contains achter (eight) single germanate chains and is composed of [UGe] heptamers and [UGe] pentamers. The structure of Cs(UO)GeO with hexagonal 10-ring channels is composed of [UGe] heptamers and twisting five-fold GeO tetrahedra in four-membered GeO rings occur. 3D frameworks of NaKCl(UO)(GeO) (space group Pnnm) and NaCsCl(UO)(GeO) ( P2/ c) can be constructed from the same SBUs [UGe] pentamers. Thermal stability of salt-inclusions was studied by TG and PXRD analysis. Analysis of charge density for the U-Si-O system indicates that the polymerization of silicate units reduces the cross-links of the 3D frameworks. The concept of SBUs combined with the cutting and gluing strategy was applied to understand and analyze the distinct 8-, 10-, 12-, and 14- membered channels for the uranyl germanate family. The charge density of all known 3D U-Si/Ge-O frameworks has been investigated, which shows strong correlations with chemical composition of corresponding phases. The increase of Si/O (Ge/O) ratios in silicate units results in the decrease of negative charge density. Moreover, the charge density increases with decreasing countercation size within the same Si/O ratio. The correlations can be used to predict inclusion phase formation within U-Si/Ge-O families. Raman spectra of the studied uranyl germanates were measured, and bands were assigned on the basis of structural features.

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Further Insight into Uranium and Thorium Metaphosphate Chemistry and the Effect of Nd³⁺ Incorporation into Uranium(IV) Metaphosphate

Abstract: 4 was proven by energy-dispersive X-ray spectroscopy (EDX), and the measured degree of substitution for U agrees well with the X-ray crystallography results;

Cited by 12 publications

References 33 publications

Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

Formation of Open Framework Uranium Germanates: The Influence of Mixed Molten Flux and Charge Density Dependence in U-Silicate and U-Germanate Families

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Further Insight into Uranium and Thorium Metaphosphate Chemistry and the Effect of Nd3+ Incorporation into Uranium(IV) Metaphosphate

Abstract: 4 was proven by energy-dispersive X-ray spectroscopy (EDX), and the measured degree of substitution for U agrees well with the X-ray crystallography results;

Cited by 12 publications

References 33 publications

Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

Formation of Open Framework Uranium Germanates: The Influence of Mixed Molten Flux and Charge Density Dependence in U-Silicate and U-Germanate Families

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Further Insight into Uranium and Thorium Metaphosphate Chemistry and the Effect of Nd³⁺ Incorporation into Uranium(IV) Metaphosphate