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91.
92.
Über Sesquiselenide der Lanthanoide: Einkristalle von Ce2Se3 im C‐, Gd2Se3 im U‐ und Lu2Se3 im Z‐Typ
On Sesquiselenides of the Lanthanoids: Single Crystals of C‐type Ce2Se3, U‐type Gd2Se3, and Z‐type Lu2Se3 Single crystals of lanthanoid sesquiselenides (M2Se3; here: M = Ce, Gd, Lu) are accessible through conversion of the elements (lanthanoid and selenium) in molar ratios of 2:3 within seven days at 850 °C from evacuated silica ampoules if equimolar amounts of NaCl serve as a flux. In the case of Ce2Se3 (a = 897.74(6) pm) und Gd2Se3 (a = 872.56(5) pm) the cubic C‐type (I4¯3d, Z = 5.333) forms as dark red beads, whereas the orthorhombic Z‐type (Fddd, Z = 16) emerges for Lu2Se3 (a = 1125.1(1), b = 798.06(8), c = 2387.7(2) pm) as orange‐yellow bricks. Upon oxidation of monochloride hydrides (MClHx or AyMClHx; M = Ce, Gd, Lu; x = 1; A = Li, Na; y = 0.5) with selenium in arc‐welded tantalum ampoules the same main products appear with C‐Ce2Se3 and Z‐Lu2Se3, even with a surplus of NaCl or LiCl as fluxing agent. In the case of Gd2Se3, however, black‐red needles of the orthorhombic U‐type (Pnma, Z = 4; a = 1118.2(1), b = 403.48(4); c = 1097.1(1) pm) are yielded instead of C‐Gd2Se3. C‐Ce2Se3 crystallizes in a cation‐deficient Th3P4‐type structure (Ce2S3 type) according to Ce2.667□0.333Se4 (Z = 4) or with Z = 5.333 for the empirical formula Ce2Se3. Here, Ce3+ is coordinated by eight Se2— anions trigon‐dodecahedrally. In U‐Gd2Se3 (U2S3 type) two crystallographically independent Gd3+ cations with coordination numbers of 7 (Gd1) and 7+1 (Gd2), respectively, are present, exhibiting mono‐ or bicapped trigonal prisms as coordination polyhedra. The crystal structure of Z‐Lu2Se3 (Sc2S3 type) shows two different Lu3+ cations as well, which now both reside in octahedral coordination of six Se2— anions each. 相似文献
93.
Two hydrated uranyl arsenates and a uranyl phosphate were synthesized by hydrothermal methods in the presence of amine structure-directing agents and their structures determined: (N2C6H14)[(UO2)(AsO4)]2(H2O)3, DabcoUAs, {NH(C2H5)3}[(UO2)2(AsO4)(AsO3OH)], TriethUAs, and (N2C4H12)(UO2)[(UO2)(PO4)]4(H2O)2, PiperUP. Intensity data were collected at room temperature using MoKα X-radiation and a CCD-based area detector. The crystal structures were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (DabcoUAs, TriethUAs, PiperUP) wR2=5.6%, 8.3%, 7.2% for all data, and R1=2.9%, 3.3%, 4.0%, calculated for 1777, 5822, 9119 unique observed reflections (|Fo|?4σF), respectively. DabcoUAs is monoclinic, space group C2/m, Z=2, a=18.581(1), b=7.1897(4), c=7.1909(4) Å, β=102.886(1)°, V=936.43(9) Å3, Dcalc=3.50 g/cm3. TriethUAs is monoclinic, space group P21/n, Z=4, a=9.6359(4), b=18.4678(7), c=10.0708(4) Å, β=92.282(1)°, V=1790.7(1) Å3, Dcalc=3.41 g/cm3. PiperUP is monoclinic, space group Pn, Z=2, a=9.3278(4), b=15.5529(7), c=9.6474(5) Å, β=93.266(1)°, V=1397.3(1) Å3, Dcalc=4.41 g/cm3. The structure of DabcoUAs contains the autunite-type sheet formed by the sharing of vertices between uranyl square bipyramids and arsenate tetrahedra. The triethylenediammonium cations are located in the interlayer along with two H2O groups and are disordered. Both TriethUAs and PiperUP contain sheets formed of uranyl pentagonal bipyramids and tetrahedra (arsenate and phosphate, respectively) with the uranophane sheet-anion topology. In TriethUAs, triethlyammonium cations are located in the interlayer. In PiperUP, the sheets are connected by a uranyl pentagonal bipyramid that shares corners with phosphate tetrahedra of adjacent sheets, resulting in a framework with piperazinium cations and H2O groups in the cavities of the structure. 相似文献
94.
V Babizhetskyy 《Journal of solid state chemistry》2004,177(2):415-424
Solid state phase equilibria in the ternary Gd-Si-B phase diagram have been proposed at 1270 K using X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Prior to this work, the binary systems Gd-B, Gd-Si and Si-B have also been reinvestigated. The main characteristic of the ternary diagram is the occurrence of two new ternary compounds Gd5Si2B8 and Gd5Si3B0.64. The former crystallizes in tetragonal symmetry, space group P4/mbm with unit cell parameters a=7.2665(3), c=8.2229(7) Å, the second one presents hexagonal symmetry, space group P63/mcm with unit cell parameters a=8.5080(4),c=6.4141(2) Å. The X-ray structures of the two structurally related phases Gd5Si3B0.64 and host binary Gd5Si3 have been refined from three-dimensional single-crystal intensity data to the final R values of 0.036 (Rw=0.046) and 0.046 (Rw=0.055) for 457 and 401 reflections, respectively with [F>4σ(F)]. Both structures exhibit the Mn5Si3-type structure, with in addition for Gd5Si3B0.64 a partial occupancy by boron of the normally vacant interstitial site at the center of the Gd6 octahedron, which corresponds to the origin of the unit cell. Bonding between the interstitial boron atoms and the gadolinium ones forming the Gd6B polyhedra is indicated by the decrease in the corresponding Gd-Gd distances and consequently in the unit cell volume. Finally, the Gd-Si-B phase diagram is compared with the previously reported Er-Si-B, at 1070 K. 相似文献
95.
Richards模型在蔬菜生长预测中的应用 总被引:6,自引:0,他引:6
本文从 Richards模型的数学表达出发 ,阐述了模型中各参数初始值的确定以及优化过程 .并利用菜花和菠菜的试验数据建立其“最优”生长模型 . 相似文献
96.
Jacquelyn A. Carioscia Lauren Schneidewind Casey O'Brien Robert Ely Caitlin Feeser Neil Cramer Christopher N. Bowman 《Journal of polymer science. Part A, Polymer chemistry》2007,45(23):5686-5696
The ability to prepare high Tg low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (Tg) for several thiol–norbornene materials. Results indicate that Tgs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high Tg materials. In particular, as much as a 70 °C increase in Tg was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007 相似文献
97.
Hong Mao-Chun Huang Zhi-Ying Cao Rong Jiang Fei-Long Liu Han-Qin State Kev Laboratory of Structural Chemistry and Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou Fujian 《结构化学》1993,(5)
<正> [Au13Ag12(μ-Br)1(μ3-Br)2 (Ph3P)10Br2] Br, monoclinic. space group C2/m, a = 36. 496(17). b=16. 878(7), c-=19. 772(9) A , β=99. 87(5)°, V=11998. 9 A3.Z=2. The final R(Rw) is 0. 097(0. 109) for 3779 reflections with I>3σ(I). The structure can he considered as two icosahedral cluster units (AurAg6) sharing one vertex and linked hy six bromine atoms. The Au - Au, Au - Ag. and Ag-Ag distances fall in the ranges of 2. 69-2. 96. 2. 84-3. 02. and 2. 92-3. 26 A, respectively. 相似文献
98.
Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re2(CO)9NCCH3 was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re2(CO)9PH3, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re2(CO)9PH3 led to the new bi- and trinuclear complexes Re2(μ-H)(μ3-PHRe(CO)5)(CO)8, Re2(μ-PH2)2(CO)8 and Re2(μ-H) · (μ-PH2)(CO)8, which were characterized by IR-, 1H- and 31P-NMR spectroscopy. The structures of ax-Re2(CO)9PH3, Re2(μ-H)(μ3-PHRe(CO)5)(CO)8 and Re2(μ-PH2)2(CO)8 were confirmed by single-crystal X-ray analysis. ax-Re2(CO)9PH3 has a very short Re? P bond length of 228(2) pm. 相似文献
99.
关于多项式系数微分方程复振荡理论的两个结果 总被引:2,自引:0,他引:2
本文证明了:如果ak-j(j=1,…,k)为多项式,degak-j=nk-j,存在某个ak-s(1≤s≤k)满足:当1≤j<s时,nk-j/j≤nk-s/s;当s<j≤k时,nk-j<nk-s-(j-s).如果F≠0是整函数且满足σ(F)=β<(nk-s+s)/s,那么微分方程f(k)+a 相似文献