Cs8UIV(UVIO2)3(Ge3O9)3·3H2O: A Mixed-Valence Uranium Germanate with 9-Ring Channels

Nguyen, Quang Bac; Liu, Hsin Kuan; Chang, Wen Jung; Lii, Kwang Hwa

doi:10.1021/ic200508v

Cited by 34 publications

(16 citation statements)

References 24 publications

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“…The supercritical hydrothermal method has proven to be very useful to crystal growth. Our long-term exploratory synthesis under hydrothermal conditions at 500–600 °C has led to a great number of new silicates and germanates of uranium in unusual valence states. − In addition to U(VI) compounds, , we reported the first U(V) silicate, K(UO)Si 2 O 6 , and a good number of mixed-valence compounds such as U(IV,V) silicate, U(IV,VI) germanate, U(V,VI) germanates, a salt-inclusion U(V,VI) silicate, and a U(IV,V,VI) silicate . The latter one is extraordinary in that three unique sites corresponding to three different valence states coexist in the structure.…”

Section: Introductionmentioning

confidence: 99%

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A₂[(UO₂)Si₄O₁₀] (A = Na, K, Rb, Cs)

Liu

Peng

Chang

et al. 2016

Crystal Growth & Design

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Four new uranyl silicates with the same framework composition but different crystal structures, Na2[(UO2)Si4O10]·0.5H2O (1), K2[(UO2)Si4O10] (2), Rb2[(UO2)Si4O10] (3), and Cs2[(UO2)Si4O10] (4), have been synthesized under supercritical hydrothermal conditions at 590 °C and 1620 bar and characterized by single-crystal X-ray diffraction and infrared and photoluminescence spectroscopy. Crystal data for compound 1: tetragonal, I4/mcm (No. 140), a = 18.0332(7) Å, c = 7.7752(5) Å, V = 2528.5(2) Å3, Z = 8, R 1 = 0.0447; compound 2: monoclinic, P21/n (No. 14), a = 8.2970(17) Å, b = 7.7403(15) Å, c = 8.7906(18) Å, β = 104.83(3)°, V = 545.74(19) Å3, Z = 2, R 1 = 0.0140; compound 3: monoclinic, P21/c (No. 14), a = 10.3483(3) Å, b = 23.7297(6) Å, c = 7.6278(2) Å, β = 110.482(1)°, V = 1754.68(8) Å3, Z = 6, R 1 = 0.0194; compound 4: orthorhombic, Cmca (No. 64), a = 7.7157(3) Å, b = 19.8719(8) Å, c = 24.0160(10) Å, V = 3682.3(3) Å3, Z = 12, R 1 = 0.0277. The silicate anions in the structures of these compounds form tubular chains, single layers, and multiple chains which are linked by UO6 tetragonal bipyramids to form three-dimensional frameworks. The tubular chains and single layers are of the new type with respect to the sequence of vertex orientations. The multiple chain is observed for the first time and contains Q 2, Q 3, and Q 4 Si. The structures of these silicate anions can be correlated with the sizes of alkali metal cations.

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Section: Introductionmentioning

confidence: 99%

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A₂[(UO₂)Si₄O₁₀] (A = Na, K, Rb, Cs)

Liu

Peng

Chang

et al. 2016

Crystal Growth & Design

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“…Of particular interest were the phosphite studies showing the control over reduction by adjusting time and pH, yielding partially reduced and fully reduced U 4+ species. This study represents one of the only systematic explorations of in situ hydrothermal reduction. , There have been a few other examples of in situ hydrothermal reduction using a variety of reducing agents and metals. − Note that these studies were unable to access oxidation states that have negative reduction potentials versus normal hydrogen electrode (NHE).…”

Section: Introductionmentioning

confidence: 99%

Straightforward Reductive Routes to Air-Stable Uranium(III) and Neptunium(III) Materials

et al. 2014

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Studies of trivalent uranium (U(3+)) and neptunium (Np(3+)) are restricted by the tendency of these ions to oxidize in the presence of air and water, requiring manipulations to be carried out in inert conditions to produce trivalent products. While the organometallic and high-temperature reduction chemistry of U(3+) and, to a much smaller extent, Np(3+) has been explored, the study of the oxoanion chemistry of these species has been limited despite their interesting optical and magnetic properties. We report the synthesis of U(3+) and Np(3+) sulfates by utilizing zinc amalgam as an in situ reductant with absolutely no regard to the exclusion of O2 or water. By employing this method we have developed a family of alkali metal U(3+) and Np(3+) sulfates that are air and water stable. The structures, electronic spectra, and magnetic behavior are reported.

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“…24 Recently, Lii and co-workers reported a number of uranium germanates prepared by high-temperature and high-pressure hydrothermal synthetic method and investigated their crystal structure as well as luminescence properties. [25][26][27][28] Importantly, these compounds mentioned above can not be obtained under mild hydrothermal conditions.…”

Section: Introductionmentioning

confidence: 99%

High-temperature, high-pressure hydrothermal synthesis, crystal structure and photoluminescent properties, of K₃[Gd_1−xTb_xGe₃O₈(OH)₂] (x = 0, 0.3, 0.1, 1)

Liu

Yang

et al. 2014

RSC Adv.

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Cs₈U^IV(U^VIO₂)₃(Ge₃O₉)₃·3H₂O: A Mixed-Valence Uranium Germanate with 9-Ring Channels

Cited by 34 publications

References 24 publications

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A₂[(UO₂)Si₄O₁₀] (A = Na, K, Rb, Cs)

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A₂[(UO₂)Si₄O₁₀] (A = Na, K, Rb, Cs)

Straightforward Reductive Routes to Air-Stable Uranium(III) and Neptunium(III) Materials

High-temperature, high-pressure hydrothermal synthesis, crystal structure and photoluminescent properties, of K₃[Gd_1−xTb_xGe₃O₈(OH)₂] (x = 0, 0.3, 0.1, 1)

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Cs8UIV(UVIO2)3(Ge3O9)3·3H2O: A Mixed-Valence Uranium Germanate with 9-Ring Channels

Cited by 34 publications

References 24 publications

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A2[(UO2)Si4O10] (A = Na, K, Rb, Cs)

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A2[(UO2)Si4O10] (A = Na, K, Rb, Cs)

Straightforward Reductive Routes to Air-Stable Uranium(III) and Neptunium(III) Materials

High-temperature, high-pressure hydrothermal synthesis, crystal structure and photoluminescent properties, of K3[Gd1−xTbxGe3O8(OH)2] (x = 0, 0.3, 0.1, 1)

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Cs₈U^IV(U^VIO₂)₃(Ge₃O₉)₃·3H₂O: A Mixed-Valence Uranium Germanate with 9-Ring Channels

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A₂[(UO₂)Si₄O₁₀] (A = Na, K, Rb, Cs)

Tubular Chains, Single Layers, and Multiple Chains in Uranyl Silicates: A₂[(UO₂)Si₄O₁₀] (A = Na, K, Rb, Cs)

High-temperature, high-pressure hydrothermal synthesis, crystal structure and photoluminescent properties, of K₃[Gd_1−xTb_xGe₃O₈(OH)₂] (x = 0, 0.3, 0.1, 1)