La2-xSrxMnRuO6系统的磁性和输运性质

通过对具有双层钙太矿结构的Ｌａ２ － ｘＳｒｘＭｎＲｕＯ６ 系统的结构,磁化率和电阻率的观测,结果发现：在ｘ＝ １ ．０ 附近,发生了从具有Ｍｎ 和Ｒｕ 无序分布的立方结构到有序分布的单斜岩盐结构的结构相变;样品在低温下呈现铁磁性,而在高温下呈现顺磁性,其电阻温度关系呈现２ Ｄ 变程跳迁（ＶＲＨ） 行为;Ｌａ２ － ｘＳｒｘＭｎＲｕＯ６（１ ．０ ≤ｘ ≤２ ．０） 样品在３００Ｋ 以下呈现亚铁磁性．它们的电阻温度关系既不能用ＶＲＨ 机制来描述,也不能用单能隙的热激活跃迁机制来描述．同时对该系统的交换相互作用进行了讨论     

Synthesis and Structure of Two Keggin-Type Heteropolyanions: [VMo12O40]3n− n (1) and [H3PMoVMoVI 11O40]1− (2)

Two Keggin-type heteropolyanions were synthesized and characterized by X-ray crystal structure and elemental analysis as well as infrared spectroscopy. Both K₃[VMo₁₂O₄₀]19H₂O (1) and [N _i (H₂O)₆][H₃PMo^VMo^VI ₁₁O₄₀]₂30 H₂O (2) were prepared in aqueous solution. Compound 1 crystallized in the space group Pm-3m, a=10.6513(1) Å, V=1208.4(3) ų, Z=1. Compound 2 crystallized in the space group R-3 with a=b=13.9669(2) Å, c=42.0075(5) Å, V=7096.71(2) ų, Z=3. The compound 1 contains a {K₆VMo₁₂O₄₀} group in which six potassium ions form a regular {K₆} octahedron. The heteropolyanion [VMo₁₂O₄₀]^3– was capped by six potassium ions and enclosed by {K₆} octahedron. A three-dimensional structure was formed by the buildup of {K₃[VMo₁₂O₄₀]} _n . Compound 2 contains a one-electron reduced heteropolyanion [H₃PMo^VMo^VI ₁₁O₄₀]^1–. Ni²⁺ coordinated by six water molecules as the counter cation balances the negative charge of the molecule.     

Electrochemical Behavior and Its Electrocatalytic Activity of A P—Mo Heteropolyanion Modified ITO Electrode

ITO is a versatile material in the electronic industry because of its special transparent and conductive properties. However, there are a few reports regarding the adsorption of organic or organometallic compounds on the ITO surface1-4. The heteropolyanions are interested in the field of material science, catalytics, biology, and medicine owing to their chemical, structural, and electronic versatility5-7. One of the most important properties of polyoxometalate anions is their ability to a…     

α—钨钒硅酸钾(α—K_3H_2SiW_(11)VO_(40)·6H_2O)的晶体结构

α-K_H_3H_2SiW_(11)VO_(40)·6H_2O属六方晶系,空间群为P6_2,晶胞参数:α=b=19.084A,c=12.489A,V=3939.17A~3,Z=3;D_0=3.86gcm~(-3),Dm=3.81gcm~(-3)。晶体内含有分立的α-SiW_(11)VO_(40)~(5-)阴离子,其形状、大小类同于α-SiW_(12)O_(40)~(4-),仅是一个W原子为V原子所取代。一个V原子与十一个W原子呈无序分市,共占据十二个原子位置。三个K原子和六个结晶水的位置已经确定。     

Synthesis and Properties of Nonatungstotricobaltosilicate Isomers

Introduction Recently substituted-type of heteropolyanions has received much attention from the point of view of their catalysis. Hill, Finke, Neumann reported respectively that transition metal mono-substituted heteropolyanions PW_(11) M, P_2W_(17)M and SiW_(11) Ru have an ability to catalyze the epoxidation of olefin. We discovered that trisubstituted Keggin heteropolyanions have this property too. This paper describes the synthesis, properties of α- and β-[SiW_9O_(27)Co_3(H_2O)_3]~(10-) and its catalysis for the epoxidation of olefin by PhIO.     

新型层柱微孔材料──Ga-W9-Co3三取代柱撑ZnAl型阴离子粘土的合成、表征及催化研究

新型层柱微孔材料──Ｇａ－Ｗ_９－Ｃｏ_３三取代柱撑ＺｎＡｌ型阴离子粘土的合成、表征及催化研究张继余,余新武,张淑云,胡长文,梁兆君,王恩波（东北师范大学化学系,长春,１３００２４）关键词过渡金属,三取代,杂多阴离子,嵌入,阴离子粘土杂多化合物是具有优...     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions:[NH3(CH2)4NH3]6[Co4(HzO)2(B-α-GeW9034)2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate,[NH3(CH2)4NH3]6 [Co4(H2O)2(B-α-GeW9O34)2]·7H2O 1,was hydrothermally synthesized and characterized by IR spectra and single-crystal X-ray diffraction.The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system,space group P21/c with a=16.6073(6),b=15.3333(5),C=19.9869(7)(A),β=103.41(1)°,Mr=5481.38,V=4950.8(3)(A)3,Z=2,Dc=3.677 g/cm3,F(000)=4900,μ(MoKα)=22.165 mm-1,GOOF=1.005,the final R=0.0228 and wR=0.0527.The crystal structure indicates that the[Co4(H2O)2(B-α-GeW9O34)2]12-polyoxoanion contains two trivacant Keggin[B-α-GeW9O34]10-fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement(C2h symmetry)leading to a sandwich-type structure.     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions： [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate, [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O 1, was hydrothermaUy synthesized and characterized by IR spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system, space group P21/c with a = 16.6073（6）, b = 15.3333（5）, c = 19.9869（7） A, β = 103.41（1）°, Mr = 5481.38, V = 4950.8（3） A3, Z = 2, Dc = 3.677 g/cm^3, F（000） = 4900, μ（MoKa） = 22.165 mm^-1, GOOF = 1.005, the final R = 0.0228 and wR = 0.0527. The crystal structure indicates that the [Co4（H2O）2（B-α-GeW9O34）2]^12- polyoxoanion contains two trivacant Keggin [B-α-GeW9O34]^10- fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement （C2h symmetry） leading to a sandwich-type structure.     

三缺位杂多阴离子α—A—PW9O34^9—的苯基硅衍生物的合成和晶体结构

合成了三缺位杂多阴离子的苯基硅衍生物 (TBA) 3[α-A-PW9O34 (Ph Si O) 3(Ph Si) ]· 2 H2 O(记为 1 ,TBA为四丁基铵阳离子 ) ,并由元素分析、红外光谱、紫外光谱对化合物进行了表征 ,研究了化合物的热性质 .结构分析结果表明 ,该化合物属三方晶系 ,空间群 R3,晶胞参数 a=1 .41 696(1 6) nm,b=1 .42 1 63 (1 6)nm,c=1 .41 661 (1 6) nm,α=99.80 1 (1 7)°,β=99.843 (1 7)°,γ=99.844(1 7)°,V=2 .71 1 1 (5 ) nm3.Z=1 ,R=0 .0 5 48.该化合物的阴离子是由 1个α-A-PW9单元 ,通过 6个 W— O— Si桥键与 3个 Ph Si O单元相连 ,3个 Ph Si O又通过 Si— O— Si桥键与另 1个处于帽位的 Ph Si相连 ,形成饱和闭合笼形结构     

[{(NiOH)2Mo10O36(PO4)Ti2}n]: a novel chainlike trimetal heteropolyanion based on pseudo-keggin fragments

A new mixed Mo/Ni/Ti heteropoly compound [C₅H₅NH]₅ [(NiOH)₂Mo₁₀O₃₆(PO₄)Ti₂] has been hydrothermally synthesized and structurally determined by the single-crystal X-ray diffraction. Black prismatic crystals crystallize in the monoclinic system, space group P2(1)/n, a=11.2075(2), b=37.8328(5) c=13.0888(1) Å, β=101.4580(10)°, M=2276.13, V=5439.19(13) ų, Z=4. Data were collected on a Siemens SMART CCD diffractometer at 293(2) K in the range of 1.68<θ<25.09° using the ω-scan technique (λ=0.71073 Å R(F)=0.0872 for 9621 reflections). The title compound contains a trimetal heteropolyanion polymer and “trans-titanium”-bridging pseudo-Keggin fragments linked to a chain.