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1.
《中国化学快报》2022,33(7):3527-3530
Two tetravalent uranium silicate and germanate M2UIVT3O9 (M = K, Cs; T = Si, Ge) crystals were crystalized under inert gas by molten salt flux growth method. K2USi3O9 (1) crystallizes in the monoclinic space group P121/n1 with lattice parameters a = 7.1076 Å, b = 10.4776 Å, c = 12.2957 Å, γ = 120° and V = 915.67 Å3. Cs2UGe3O9 (2) crystallizes in a hexagonal space group P-6 with lattice constants of a = 7.5138 Å, b = 7.5138 Å, c = 11.0114 Å, γ = 120° and V = 538.38 Å3. Bond valence calculations indicate tetravalent uranium in both structures, which contain three-membered single-ring T3O96? trimers. K2USi3O9 is the first uranium silicate that contains the Si3O96? trimers. 相似文献
2.
A very rare tetravalent uranium germanate has been synthesized under hydrothermal conditions at 585 °C and 160 MPa. Its structure contains layers of single-ring Ge(3)O(9)(6-) germanate anions that are connected by UO(6) octahedra and dimers of edge-sharing GeO(5) trigonal bipyramids to form a three-dimensional framework with intersecting 6- and 7-ring channels. UV-visible, photoluminescence, and U 4f X-ray photoelectron spectroscopy were used to confirm the valence state of uranium. 相似文献
3.
A new uranium(IV) fluorooxalate, UF3(H2O)(C2O4)0.5, has been synthesized by a hydrothermal method and structurally characterized by single-crystal X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The structure consists of two-dimensional layers of corner- and edge-sharing tricapped trigonal prisms with the composition UF(4/2)F(2/2)O3 linked by bisbidentate oxalate ligands to form a three-dimensional framework. Magnetic susceptibilities were measured to confirm the tetravalent state of uranium. Crystal data: monoclinic, space group C2/c, a = 17.246(3) Angstroms, b = 6.088(1) Angstroms, c = 8.589(2) Angstroms, beta = 95.43(3) degrees, and Z = 8. 相似文献
4.
Maria Wierzbicka-Wieczorek Martin Goeckeritz Uwe Kolitsch Christoph Lenz Gerald Giester 《ChemInform》2015,46(30):no-no
Single crystals of Cs1.86K1.14DySi6O15 (I) and Cs1.6K1.4SmSi6O15 (II) are grown by reaction of SmF3 or Dy2O3, DyF3, SiO2, K2CO3, and Cs2CO3 in a MoO3 or MoO3/RbF flux (Pt crucible, 950 °C, 3—6 h; controlled cooling). 相似文献
5.
We report the first example of pentavalent-uranium silicate synthesized by a high-temperature, high-pressure hydrothermal method. The 3-D framework consists of four-membered single rings of corner-sharing SiO4 tetrahedra and 1-D UO4/1O2/2 chains. Magnetic susceptibility and XPS were measured to identify the valence state of uranium. 相似文献
6.
A. E. Lapshin N. V. Borisova V. M. Ushakov Yu. F. Shepelev 《Russian Journal of Inorganic Chemistry》2006,51(11):1696-1700
Crystals of cesium silicate Cs6Si10O23 were prepared upon the crystallization of glass Cs2O · 4SiO2. The crystal structure of Cs6Si10O23 was determined by single-crystal X-ray diffraction (space group P $\bar 6$ 2m, a = 9.578(5) Å, c = 4.155(5) Å, Z = 0.5, 269 F(hkl), R = 0.0424). The three-dimensional tetrahedral silicate framework in Cs6Si10O23 is similar to that in Rb6Si10O23 (space group P $\bar 6$ 2m, a = 9.475(5) Å, c = 8.200(5) Å) in which layers formed by 12-membered rings of silicon-oxygen tetrahedra may be distinguished. However, while in the rubidium silicate structure the vertices of the tetrahedra neighboring in a layer point to opposite directions, in cesium silicate these tetrahedra are disordered as regards the arrangement of vertices either upward or downward relative to the layer plane. The random disorder results in a smaller unit cell parameter c in Cs6Si10O23 compared to Rb6Si10O23. The compound melts congruently; the melting temperature and the enthalpy of melting of the crystal are 1208 ± 1 K and 156.2 ± 15 kJ/mol, respectively. 相似文献
7.
New Alkali Cyclosilicates: Cs5AgSi3O9 and Cs6Na6Si6O18 The new cyclosilicates were obtained from reactions of the binary oxides at 450–500 °C under inert gas atmosphere. Cs5AgSi3O9 crystallizes in the space group P21/m with the lattice constants a = 968,2(2) pm, b = 652,7(1) pm, c = 1162,6(3) pm, β = 93,84(2)° and Cs6Na6Si6O18 in R‐3m with a = 1208,0(1) pm, c = 1458,9(2) pm (IPDS data sets). The characteristic features are isolated rings, [Si3O9]6– and [Si6O18]12–, respectively. In Cs5AgSi3O9 these are connected via Ag+ to chains. Layers of [NaO4]‐tetrahedra separate the hexameric rings in Cs6Na6Si6O18. Coordination numbers of caesium are observed between C.N. 3 and C.N. 9 in these alkali rich cyclosilicates. MAPLE calculations of both cyclosilicates as well as the absorption and IR spectrum of Cs5AgSi3O9 are presented. Preparative and thermoanalytical techniques have been used to investigate the reactivity of Cs5AgSi3O9 in the presence of cobalt and nickel metal. 相似文献
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New Metal Oxides with Doubles of Tetrahedra as Building Units: Rb6[Tl2O6] and Cs6[In2O6] We prepared the hitherto unknown Rb6[Tl2O6] and Cs6[In2O6] by heating mixtures of Tl2O3 and RbO0.60 (Rb:Tl = 3.5:1) as well as In2O3 and CsO0.53 (Cs:In = 3.5:1) as single crystals [closed Ag-cylinder, 650°C, 14 d]. The single crystals of Rb6[Tl2O6] are yellow, those of Cs6[In2O6] pale yellow, all transparent and rude. The new type of structure was elucidated by 4-circle-diffractometer (PW 1100) data. Rb6[Tl2O6]: P21/a; a = 1145,7(3), b = 713,3(1), c = 783,9(2) pm, β = 93,73° (2), Z = 2; Ag–Kα, 2100 out of 2531 I0(hkl), R = 9,6% and Rw = 8,9%. Cs6[In2O6]: P21/a; a = 1178,5(4), b = 730,7(2), c = 816,3(2) pm, β = 95,38° (3), Z = 2; Mo–Kα, 1584 out of 2032 I0(hkl), R = 9,25%, and Rw = 8,44%. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed. 相似文献
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A new mixed-valence uranium germanate and the silicate analogue have been synthesized under hydrothermal conditions at 600 °C and 165 MPa. Their crystal structures contain infinite -U(V)-O-U(IV/V)-O-U(IV/V)-O-U(V)- chains that are connected by Ge(2)O(7) or Si(2)O(7) groups to form a 3D framework with six-ring channels where the Cs(+) cations are located. Two of the Cs sites in the germanate are partially occupied. Bond-valence-sum calculation and an U 4f X-ray photoelectron spectroscopy study confirm the valence states of the uranium. 相似文献
13.
A pentavalent uranium germanate, Cs(3)UGe(7)O(18), was synthesized under high-temperature, high-pressure hydrothermal conditions at 585 °C and 160 MPa and structurally characterized by single-crystal X-ray diffraction and infrared spectroscopy. The valence state of uranium was confirmed by X-ray photoelectron spectroscopy and electron paramagnetic resonance. The room-temperature EPR spectrum can be simulated with two components using an axial model that are consistent with two distinct sites of uranium(V). In the structure of the title compound, each ([6])GeO(6) octahedron is bonded to six three-membered single-ring ([4])Ge(3)O(9)(6-) units to form germanate triple layers in the ab plane. Each layer contains nine-ring windows; however, these windows are blocked by adjacent layers. The triple layers are further connected by UO(6) octahedra to form a three-dimensional framework with intersecting six-ring channels along the <1 ?10> directions. The Cs(+) cation sites are fully occupied, ordered, and located in the cavities of the framework. Pentavalent uranium germanates or silicates are very rare, and only two uranium silicates and one germanate analogue have been published. However, all of them are iso-structural with those of the Nb or Ta analogues. In contrast, the title compound adopts a new structural type and contains both four- and six-coordinate germanium. Crystal data of Cs(3)UGe(7)O(18): trigonal, P3?c1 (No. 165), a = 12.5582(4) ?, c = 19.7870(6) ?, V = 2702.50(15) ?(3), Z = 6, D(calc) = 5.283 g·cm(-3), μ(Mo Kα) = 26.528 mm(-1), R(1) = 0.0204, wR(2) = 0.0519 for 1958 reflections with I > 2σ(I). GooF = 1.040, ρ(max,min) = 1.018, and -1.823 e·?(-3). 相似文献
14.
A new cobalt-indium silicate, Rb6(InCo)2(Si9O26), has been synthesized via a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. It crystallizes in the noncentrosymmetric orthorhombic space group Aba2 (No. 41) with a = 20.779(1) A, b = 12.0944(6) A, c = 10.7761(5) A, V =2708.1(2) A(3), and Z = 4. The structure consists of 20-membered-ring silicate single layers of corner-sharing SiO4 tetrahedra interconnected by dimers of edge-sharing CoO4 tetrahedra and InO6 octahedra into a 3D framework. The Si:O ratio for the title compound is the lowest among the known single-layer silicates. Magnetic susceptibility confirms the divalent state of the cobalt ion. The powder sample has a second-harmonic-generation signal, confirming the absence of a center of symmetry in the structure. 相似文献
15.
Volkringer C Mihalcea I Vigier JF Beaurain A Visseaux M Loiseau T 《Inorganic chemistry》2011,50(23):11865-11867
An uranium trimesate open framework is built up from trinuclear building blocks (μ(3)-OU(3)) connected to each other by tricarboxylate linkers to generate honeycomb-like 3D topology. This compound was solvothermally synthesized from low-valent uranium in an N,N-dimethylformamide solvent under an inert atmosphere, favoring stabilization of the tetravalent oxidation state, which is confirmed by X-ray photoelectron spectroscopy analysis. 相似文献
16.
《Chemical physics letters》1987,138(1):23-28
The luminescences of Cs2NaSbCl6 and Cs2NaSbBr6 are reported. For Cs2NaSbBr6 the luminescence properties are described in terms of a band model. For Cs2NaSbCl6 the luminescence is interpreted in terms of isolated Sb3+ centres, comparable with Cs2NaMCl6−Sb3+ (M = Sc, Y, La). The radius of the Sb3+ ion is larger in the chloro- than in the bromo-elpasolite. 相似文献
17.
On Hexafluoroferrates(III): Cs2TlFeF6, Cs2KFeF6, Rb2KFeF6, Rb2NaFeF6, and Cs2NaFeF6 New prepared are the compounds Cs2TlFeF6 (a = 9.211 Å), Cs2KFeF6 (a = 9.041 Å), Rb2KFeF6 (a = 8.868 Å) and Rb2NaFeF6 (a = 8.46 4Å) all cubic Elpasolithes as well as Cs2NaFeF6 (Cs2NaCrF6?type, hexagonal with a = 6.281, c = 30.532 Å), all colourless. Cs2KFeF6 was measured magnetically (70–297,2 K). The spectra of reflection were measured (9000–36000 cm?1). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed. 相似文献
18.
Malliakas CD Yao J Wells DM Jin GB Skanthakumar S Choi ES Balasubramanian M Soderholm L Ellis DE Kanatzidis MG Ibers JA 《Inorganic chemistry》2012,51(11):6153-6163
Black single crystals of A(6)Cu(12)U(2)S(15) (A = K, Rb, Cs) have been synthesized by the reactive flux method. These isostructural compounds crystallize in the cubic space group Ia ?3d at room temperature. The structure comprises a three-dimensional framework built from US(6) octahedra and CuS(3) trigonal planar units with A cations residing in the cavities. There are no S-S bonds in the structure. To elucidate the oxidation state of U in these compounds, various physical property measurements and characterization methods were carried out. Temperature-dependent electrical resistivity measurement on a single crystal of K(6)Cu(12)U(2)S(15) showed it to be a semiconductor. These three A(6)Cu(12)U(2)S(15) (A = K, Rb, Cs) compounds all exhibit small effective magnetic moments, < 0.58 μ(B)/U and band gaps of about 0.55(2) eV in their optical absorption spectra. From X-ray absorption near edge spectroscopy (XANES), the absorption edge of A(6)Cu(12)U(2)S(15) is very close to that of UO(3). Electronic band structure calculations at the density functional theory (DFT) level indicate a strong degree of covalency between U and S atoms, but theory was not conclusive about the formal oxidation state of U. All experimental data suggest that the A(6)Cu(12)U(2)S(15) family is best described as an intermediate U(5+)/U(6+) sulfide system of (A(+))(6)(Cu(+))(12)(U(5+))(2)(S(2-))(13)(S(-))(2) and (A(+))(6)(Cu(+))(12)(U(6+))(2)(S(2-))(15). 相似文献
19.
A new uranium(V) silicate, K3(U3O6)(Si2O7), and the germanate analogue, Rb3(U3O6)(Ge2O7), have been synthesized under high-temperature, high-pressure hydrothermal conditions and characterized by single-crystal X-ray diffraction. Their structures contain uranate columns formed of triple octahedral chains of the alpha-UF5 type linked by disilicate (or digermanate) units to form a 3-D framework structure. The valence state of uranium is confirmed by X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and magnetic susceptibility. 相似文献
20.
New Oxogallates of Alkaline Metals: On K6[Ga2O6] and Rb6[Ga2O6] as well as Na3GaO3 and Cs6[Ga2O6] Due to powder and single crystal data K6[Ga2O6] a = 7.099; b = 11.116; c = 6.484 Å; ß = 101.66° and Rb6[Ga2O6] a = 7.393; b = 11.475; c = 6.798 Å; ß = 103.5° crystallize isotypic with K6[Fe2O6]; space group C2/m-C32h; As well has been prepared the hitherto unknown Na3GaO3 a = 11.48, b = 10.82, c = 6.13 Å, space-group Imcm or I2cm Z = 8; and Cs6[Ga2O6] a = 7.26, b = 12.1, c = 7.68 Å, ß = 105°, Z = 4, space-group P21/a. 相似文献