NaSn2(PO4)3的水热合成与结构性能研究

应用水热合成技术制备了具有NASICON型结构的NaSn₂(PO₄)₃离子导体.研究了其结构与电导性能.结果表明,水热合成制备NaSn₂(PO₄)₃离子导体化合物,是一条新的途径,它比传统的高温固相反应方法更加方便有效,尤其容易获得较纯的物相及单晶,并且水热晶化产物与固相反应产物具有相同的结构和性能.     

Synthesis,Structure and Reaction of a New Bitungsten Compound:(Et_4N)_2W_2S_4 (tdt)_2

1INTRODUCTION'TheclusterscontainingMo--SorW--Shavebeenstudiedextensivelyfortheirimportantapplicationsinmanyfieldsll~43.Alongwith.thedevelopmentofrationaldesignedsynthesissuchasthe"UnitConstruction"utilizingwell-definedactivecom-poundsasbuildingblocks,binuclearsulfidecompoundsusedtodesignnewclustershavebeenpaidattentiontots'6itandalotofcompoundscontainingiM,S.O.--.J' (M=MoorW)coreshavebeenprepared['i.Inthispaper,thefirstexamplpofbitung-stencompoundwithtdtZ--ligands(Et.N),W,S.(tdt),,…     

具有螺旋结构的新型硼磷酸盐化合物:(NH_4)_(0.5)(H_3O)_(0.5)Mg(H_2O)_2BP_2O_8

利用水热方法合成新型硼磷化合物 (NH4) 0 .5(H3 O) 0 .5Mg(H2 O) 2 BP2 O8,单晶X射线衍射分析证明化合物属六方晶系 ,空间群为P652 2 ,a =0 .945 0 7( 19)nm ,c=1.5 80 3 ( 5 )nm ,γ =12 0° ,V =1.2 2 2 4( 5 )nm3 ,Mr=2 79.0 6,Dc=2 .2 5 8g/cm3 ,Z =6,F( 0 0 0 ) =83 4,μ =0 .663mm-1.结构中BO4,PO4基团形成1∞{[BP2 O8] 3 -}的螺旋带与MgO6相连构成八面体 -四面体空间骨架 ,元素分析、IR光谱、热重差热分析和电荷平衡计算证明晶体中含有NH+ 4 和质子 .NH+ 4 占据螺旋带螺旋纹内 ,质子化的水分子靠近螺旋带通道的内侧 ,两者均起到平衡电荷和稳定骨架的作用     

具有螺旋结构的新型硼磷酸盐化合物:(NH4)0.5(H3O)0.5Mg(H2O)2BP2O8

利用水热方法合成新型硼磷化合物:(NH4)0.5(H3O)0.5Mg(H2O)2BP2O8,单晶X射 线衍射分析证明化合物属六方晶系,空间群为P6522,a=0.94507(19)nm,c=1.5803(5) nm,γ=120°,V=1.2224(5)nm^3,Mr=279.06,Dc=2.258g/cm^3,Z=6,F(000)=834,μ =0.663mm^-1。结构中BO4,PO4基团形成∞^1{[BP2O8]^3-}的螺旋带与MgO6相连构 成八面体-四面体空间骨架,元素分析、IR光谱、热重差热分析和电荷平衡计算证 明晶体中含有NH4^+和质子。NH4^+占据螺旋带螺旋纹内,质子化的水分靠近螺旋带 通道的内侧,两者均起到平衡电荷和稳定骨架的作用。     

化合物[H（1,8—萘啶氮氧化物）2]ClO4的合成及其结构研究

对于芳香胺及其氮氧化物与氢离子形成的化合物[H(Phen)_2]ClO_4、[H(napy)_2]ClO_4、[H(pyo)_2]ClO_4(Phen:邻菲啰啉,napy:1,8-萘啶,pyo:吡啶氮氧化物)等的研究,以往的工作主要限于测定稳定常数和光谱,而对它们的结构尚未进行研究。属于芳香胺氮氧化物类的1,8-萘啶氮氧化物(简称napyo)与金属离子具有很好的配位作用。为了研究napyo同氢离子的作用情况,我们在甲醇介质中制备出未见报道的[H(napyo)_2]ClO_4单晶,研究了它的晶体结构和电子结构。     

NaZr2（PO4）3的水热晶化研究

NaZr_2(PO_4)_3是一种具有典型骨架结构的离子导体化合物。它的制备一般都采用高温固相反应的方法。这种方法反应温度高,容易产生杂晶,特别是有其它聚合态的磷酸盐生成。Clearfield等曾报道,在水热条件下从α-ZrP(Zr(HPO_4)_2·H_2O)可间接制备NaZr_2(PO_4)_3,但所得产物也不是完全的纯相。我们在水热条件下,直接晶化却得到完全纯的NaZr_2(PO_4)_3相及其单晶。     

A Pseudo-Keggin Compound: Hydrothermal Synthesis and Crystal Structure of (DETAH)(DETAH_3)_3[V_(18)O_(42)(PO_4)]·(PO_4)·2H_2O

The novel vanadophosphate (DETAH)(DETAH3)3[V18O42(PO4)]·(PO4)·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857(3), b = 12.9619(18), c = 20.204(3) , β = 105.692(2)°, V = 6015.0(14) 3, Z = 4, Dc = 2.473 g/cm3, Mr = 2239.68, F(000) = 4432, R = 0.0725, wR = 0.1524 and GOOF = 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO43- guest.     

Na_（1＋x）Al_xZr_（2－x）P_3O_（12）的水热合成与表征

采用水热法合成了系列磷酸盐化合物Ｎａ_（１＋ｘ）Ａｌ_ｘＺｒ_（２－ｘ）Ｐ_３Ｏ_（１２），该系列化合物具有ＮＡＳＩＣＯＮ型三维骨架结构。考查了反应物料配比、晶化时间、晶化温度等实验条件对产物物相及掺入Ａｌ含量对化合物的结构与性能的影响．实验结果表明：在０≤ｘ≤０．３３的范围内，可水热合成出Ｎａ_（１＋ｘ）Ａｌ_ｘＺｒ_（２－ｘ）Ｐ_３Ｏ_（１２）纯相，而且具有良好的热稳定性。该系列化合物的离子电导率测试结果表明，其电导率与掺入的Ａｌ含量有关。     

Synthesis,Crystal Structure and Photoluminescence Property of Potassium Terbium Polyphosphate KTb(PO_3)_4

The potassium terbium polyphosphate crystal KTb(PO_3)_4 has been synthesized using a high temperature solution reaction method. The structure and composition were characterized by single-crystal X-ray diffraction, powder X-ray diffraction and elemental analysis. The compound crystallizes in the monoclinic space group P21/n with a=10.3182(6), b=8.9129(5), c=10.7940(6) ?, β=105.993(1)o, V=954.3 ?~3, Z=4, Mr=513.91, Dc=3.577 g/cm~3, μ=8.585 mm~(-1), F(000)=960, S=0.955,(Δρ)max=1.380,(Δρ)min=–3.428 e/?~3, the final R=0.0301 and w R=0.0400 for 2301 observed reflections with I 2σ(I). In addition, pure powder of isostructural Rb Tb(PO_3)_4 was synthesized in order to investigate the optical property. Photoluminescence measurements show that both crystals ATb(PO_3)_4(A=K(1), Rb(2)) are promising candidates to become solid-state visible green light-emitting sources.     

Synthesis,Structure, and Magnetic Properties of a New Selenite Compound CdNi(SeO_3)_2(H_2O)_2

A new selenite compound CdNi(SeO_3)_2(H_2O)_2 has been obtained by a conventional hydrothermal method. This compound crystallizes in monoclinic system of space group C2/c, which exhibits a layer structure built by NiO_6 octahedra and SeO_3 trigonal pyramids running along the a-axis. The layers show a unique eight-rings hole network. The compound is stable at room temperature while the loss of H_2O molecules happens with heating above 523 K. Magnetic measurements indicate that CdNi(SeO_3)_2(H_2O)_2 is an antiferromagnet and possesses an antiferromagnetic ordering at T_N = 15 K.     

Synthesis,Structure and Photophysical Properties of a New Complex:Co_(0.5)Ni_(0.5)(C_2H_6N_2O)_6SO_4

A new complex,Co_(0.5)Ni_(0.5)(C_2H_6N_2O)_6SO_4(Ⅰ), was synthesized and its single crystal was obtained from aqueous solution by evaporating solvent slowly. Single-crystal X-ray analysis revealed that the complex belongs to trigonal system, space group R-3c, with a = b = 10.999(2) ?, c = 40.439(13) ?, V = 4237(2) ?~3, Z = 6, D_c = 1.410 g/cm~3, M_r = 599.41, μ = 0.785 mm~(-1), F(000) = 1893, the final R = 0.0330 and wR = 0.0926(I 2σ(I)). IR spectrum and compositional analyses(elemental analyzer and ICP) were used to characterize the composition of the product. TGA(Thermal Gravimetric Analysis) showed that complex Ⅰ remained stable until it is heated up to 200 ℃, indicating its good thermostability. The main transmission peak of complex Ⅰ in UV-Vis spectrum appeared at 290 nm, making it an eligible material for ultraviolet light filters(ULF).     

SYNTHESES AND CRYSTAL STRUCTURES OF (Et_4N)_2(Fe_2Se_2(SPh)_4) AND (Et_4N)_2(Fe_4Se_4Cl_4)

<正> Since the discovery of iron-sulfur proteins , a number of analogous compounds of the active sites of iron-sulfur proteins has been synthesized and characterized . Due to the similarity between sulfur and selenium, some selenoproteins with similar active site as iron-sulfur proteins were found . We have synthesized a series of iron-selenium compounds in correlative study with the iron-sulfur compounds. In this paper, we will discuss the syntheses and crystal stuctures of the title compounds. The spectroscopic properties of these compounds have been under investigation.     

Crystal Growth,Preparation, Structure and Electrochemical Properties of Alluaudite-type NaMnV_2(PO_4)_3

Alluaudite-type NaMnV2(PO4)3 single crystal was successfully synthesized in the NaCl molten-salt media. The single-crystal diffraction data analysis shows that NaMnV2(PO4)3 crystallizes in monoclinic C2/c space group with a = 12.098(2), b = 12.415(2), c = 6.4543(11) ?, β = 114.614(2)°, V = 881.3(3) ?3, Mr = 464.64, Dc = 3.50158 g/cm3, μ(Mo Kα) = 4.046 mm-1, F(000) = 892.4 and Z = 2. The structure consists of MnO6, VO6 octahedra and PO4 tetrahedra, which form a three-dimensional architecture with two sets of large Na+ tunnels. The intercalation/deintercalation properties of NaMnV2(PO4)3 as positive and negative electrodes were tested in sodium batteries.     

A Novel Layered Complex with Rhomboidal Channels:Hydrothermal Synthesis,Crystal Structure,and Properties of Cu(4,4''''-bipy)_2(H_2PO_4)_2(H_2O)_2 (bipy=bipyridine)

IntroductionMetalcoordinationpolymerswithvariablechan nelsorcavitiesarecurrentlyofinterestduetotheirpotentialfunctionsasmicroporoussolidmaterialsformolecularadsorption ,ionexchange ,molecularmag nets,andshape selectivecatalysis[1— 3] .Amajorre searchefforthasbeenfocusedonusingthemolecularbuildingblockapproachtogeneratesuchmicroporousmaterials[3— 5] .Beinganalogoustopyrazine ,therigidrod like 4 ,4′ bipyridine(4 ,4′ bipy)ligandisausefulbuildingblockfortheconstructionofmetal organicco ordinat…     

磷酸锡盐的水热合成及其表征

用水热合成出系列化合物ＭＳｎ２（ＰＯ４）３（Ｍ＝Ｎａ，Ｋ，ＮＨ４），该化合物具有ＮＡＳＩＣＯＮ型三维骨架结构，测得其晶胞参数为：（１）ＮａＳｎ２（ＰＯ４）３，ａ＝０．８５２６９２）ｎｍ，ｃ＝２．２４７（４）ｎｍ；（２）ＫＳｎ２（ＰＯ４）３，ａ＝０．８３６６（１）ｎｍ，ｃ＝２．３５６（４）ｎｍ；（３）ＮＨ４Ｓｎ２（ＰＯ４）３，ａ＝０＼８３３０（１）ｎｍ，ｃ＝２＼３９０（５）ｎｍ．热分析结果表明，在较     

含能配合物[Zn(DAT)_6](ClO_4)_2 (DAT=1,5-二氨基四唑)的合成、晶体结构及性质

采用直接法合成了新型高氮含能配合物[Zn(DAT)6](ClO4)2(DAT=1,5-二氨基四唑),并用元素分析、傅立叶变换红外光谱对其结构进行了表征.利用缓慢蒸发溶剂法培养出其单晶,采用X射线单晶衍射仪测定其晶体结构,结果表明该晶体属于三方晶系,P3空间群,a=b=1.18398(9)nm,c=0.65700(10)nm,γ=120°,V=0.79760(15)nm3,Z=1.在目标配合物的最小不对称单元中有1个Zn2+,6个DAT分子和2个ClO-4.来自6个DAT分子的6个N原子分别与中心Zn2+配位,形成一个六配位、非中心对称的畸变八面体结构.用差示扫描量热分析、热重-微分热重分析结合红外光谱研究了标题化合物的热分解机理以及分解反应动力学参数.测定了标题配合物的感度性能,结果表明标题配合物具有一定的摩擦感度.     

[Ho_2(phen)_4(H_2O)_4(OH)_2](phen)_2(NO_3)_4的合成、晶体结构及磁性

在甲醇与水的混合溶剂中,经浓硝酸硝化的Ho_2O_3与1,10-邻菲啰啉反应形 成氢氧根桥联的双核钬配合物[Ho_2(phen)_4(H_2O)_4(OH)_2] (phen)_2(NO_3)_4 （phen = 1,10-邻菲啰啉）。单晶X射线衍射晶体结构测定表明晶体属三斜晶系, P1-bar (no. 2)空间群,晶胞参数a = 1.1241(1) nm, b = 1.1439(1) nm, c = 1. 4058 (1) nm, α = 93.989(7)°, β = 98.173(7)°, γ = 108.19(1)°, V = 1.6874(4) nm~3, Z = 1, D_c = 1.737 g/cm~3, F(000) = 880,7752个独立衍射 点中,5702个可观测点满足F_o~2 ≥ 2σ (F_o~2),R_1 = 0.0499, wR_2 = 0. 858。标题配合物由中心对称的双核[Ho_2(phen)_4(H_2O)_4-(OH)_2]~(4+)配阳离 子,邻菲啰啉phen分子及硝酸根NO_3~-阴离子组成。敏个稀土原子与2个邻菲啰啉 配体,2相水分子和2个氢氧根配位形成配位数为8的[HoN_4O_4]四方反棱柱。配位 多面体通过两氢氧根基团形成共棱的[Ho_2N_8O_6]双四方反棱柱[d(Ho-N) = 0. 2549～0.2565 nm, d(Ho-O_(H_2O) = 0.2356, 0.2366 nm, d(Ho-O_(OH)) = 0. 2223, 0.2240 nm]。通过氢键和芳环堆积作用,配阳离子和邻菲啰啉分子排列形成 平行于（10 1-bar）的两维层结构,NO_3~-阴离子位于层之间。标题配合物为顺磁 物质,在5 ～300K区间内遵循Curie-Weiss定律X_m (T + 4.43) = 14.72 cm~3·K ·mol~(-1)(X_m为每摩尔Ho~(3+)离子磁化率）,其Ho~(3+)离子的室温有效磁矩为 10.76 B. M.,与Ho~(3+)自由离子的磁矩基本相同,表明稀土离子间不存在磁交换 作用。     

一维链状超分子化合物[Cu(dafo)_2(H_2O)_2](OPA)_2的合成和晶体结构

用4,5-二氮芴-9-酮(dafo)、邻苯二甲酸和硝酸铜合成了二价铜的一维链状超 分子化合物[Cu(dafo)_2(H_2O)_2]-(OPA)_2(OPA=邻苯二甲酸一价阴离子),其结构 通过单晶X射线衍射法确定。该化合物是单斜晶系,空间群为P2(1)/c。晶胞参数： a = 0.71093(16)nm, b = 1.5724(4)nm, c = 1.5357(3)nm, α=90.000(5) °, β =102.220(4) °,γ=90.000(5) °, V = 1.6778(6)nm~3, Z = 2, F(000) = 814, M_r = 794.17, D_c = 1.527 g/cm~3, μ = 0.727 mm~(-1), R_1 = 0.0406, wR_2 = 0.0930.单晶结构分析表明该化合物具有一维链状结构,该结构是通过氢 键这种弱相互作用形成的。     

二核钼化合物Mo_2S_4(S_2P(iprO)_2)_2的合成、反应和结构表征

二核钼化合物Mo2S4（S2P（iprO）2）2（Ⅰ）（ipr=（CH3）2CH）由（NH4）2MoS4和HS2P（iprO）2反应生成，含有1个[Mo2S4]2+簇芯。Mo-Mo键长为2．8201（8）A。除了簇芯的配位外，每个钼原子上都有1个双齿的二异丙基二硫代磷酸酯配体形成钼的四方单锥配位环境。晶体学结构数据：单科晶系，空间群P21／c，晶胞参数a=12．869（2），b=13．90（3），c=16.262（5）A，β＝101.92（3）°，V＝2856（2）A3，Z=4，R=0．044，Rw=0．057。还报道该化合物作为润滑油添加剂的性能测试结果。     

Synthesis and Crystal Structure of a Two-dimensional Sil-ver(I)-Iron(III) Heteronuclear Coordination Polymer:{[Ag_4Fe_2(SCN)_(12)(H_2O)_2][(inaH)_2(H_2O)_2]}_n

Introduction Molecules containing different kinds of metal ions play an important role in molecular magnetism.1-3 So considerable attention has been paid to synthesizing heteronuclear complexes.1-4 As a potential bridging ligand, thiocyanate can coordinate to a harder metal center and softer ones with N and S atoms respectively. The complexes of thiocyanate and representative hard acidFe(III) ions usually have a six-coordinate octahe-dral structure such as [Fe(SCN)n]3-n and (Bu4N)4[Ag2-F…