层状多硫代锑(Ⅲ)酸镉(Ⅱ)化合物(1,4-DABH2)Cd2Sb2S6的溶剂热合成与表征

利用溶剂热方法合成了层状多硫代锑髥酸镉髤化合物(1,4-DABH2)Cd2Sb2S6(1)(1,4-DAB=1,4-丁二胺),并通过红外光谱、热重分析对其进行了表征,用X-射线衍射测定了化合物的单晶结构。单晶解析表明,化合物属正交晶系,Cmca空间群,Mr=750.77,a=0.860 3(5)nm,b=0.898 7(6)nm,c=2.273(2)nm,V=1.758(2)nm3,Z=4,λ=0.071 073 nm,R=0.032,wR=0.106 7。晶体结构中含有六元环的Cd2SbS3和八元环的Cd2Sb2S4的阴离子网络层状[CdSbS3]nn-,双质子化的有机阳离子在阴离子层之间以氢键N-H…S形式连接。另外紫外-可见漫反射光谱研究表明,化合物为半导体。     

有机杂化含Te2^2-／Se3^2-过渡金属化合物的溶剂热合成及晶体结构

本文通过溶剂热法合成了2种新的有机杂化锌碲化物[Zn(dien)2](Te2)(1)和镍硒化物[Ni(dien)2](Se3)(2)(dien=二乙烯三胺),单晶X射线衍射分析结果表明,化合物1属于正交晶系,Cmca空间群,晶胞参数:a=9.212(2),b=10.854(3),c=15.723(4),Z=4。化合物2属于正交晶系,Pna21空间群,晶胞参数:a=18.047(4),b=9.8236(19),c=9.0079(19),Z=4。在两种化合物中,1的阳离子中Zn2 与2个dien螯合形成稍变形的八面体几何构型,阴离子为哑铃型的Te22-。2的阳离子中Ni2 离子与2个dien螯合形成稍变形的八面体几何构型,阴离子为‘V’字型的Se32-。     

混合价多硒代锗酸盐K2Ge4Se8的固相合成、晶体结构和反射光谱研究

采用反应性熔盐法以n(K2Se3)∶n(Ge)∶n(Se)=2∶1∶6的摩尔比,在773 K下反应5 d,得到一种新的混合价硒代锗酸盐,K2Ge4Se8.该晶体属于单斜系,空间群为P21/c,晶胞参数a=0.73752(5) nm, b=1.2239(2) nm, c=1.7468(4) nm, β=96.02(3)°, V=1.5680(5) nm3, Z=4.偏差因子R1=0.0643, wR2=0.1547. K2Ge4Se8晶体具有层状结构,二维的 2∞[Ge4Se8]2-层负离子和K+正离子堆积而成,层与层按ABAB排列.K2Ge4Se8属于Zintl型化合物,属于半导体,反射光谱法测定的光学能隙(Eg)为1.8 eV.     

沙漏型砷钼酸盐(NH_4)_7[AsMo_8O_(30)]的水热合成,结构和性质(英文)

利用水热合成法制备了一种新的沙漏型砷钼酸盐化合物(NH_1)_7[AsMo_8O_(30)](1),借助X射线单晶衍射、X射线粉末衍射、红外光谱(IR)、紫外光谱(UV)和热分析研究了化合物的结构和性质.结果表明,化合物1属于正交晶系,Cmcm空间群,晶胞参数为:a=0.848 3(4)nm,b=2.322 3(10)nm,c=1.559 1(7)nm,V=3.071(2)nm~3,Z=4,R_1[I>2σ(I)]=0.0431,ωR_2[I>2σ(I)]=0.123 6.X射线单晶衍射分析结果表明,化合物1包含沙漏型的砷钼酸盐阴离子[AsMo_9O_(30)]~(7-).     

一种新型磷酸铍微孔晶体的合成与表征

水热晶化法合成并培养一种新型磷酸铍微孔晶体。经多晶X射线衍射, 四圆X射线单晶结构分析, 红外光谱等测定, 其骨架结构是由磷氧四面体和铍氧四面体交替的, 通过共用顶点氧原子(氧桥形式)构成的阴离子骨架。晶体属正交晶系,空间群为Pna21, 晶胞参数a=0.8699(1)nm, b=0.856(1)nm, c=0.4953(2)nm, 晶胞体积V=0.3691(7)nm^3。Z=4, 求解结构中最后R=0.054, Rw=0.048。微孔体系由4,6和8元环组成。水分子和平衡阴离子骨架电荷的质子位于平行(100)方向的六元环通道中, 研究其热稳定性能。     

[Ln2（HINC）4]6+（Ln=Ce,Eu）二聚体修饰的两个Dawson型超分子化合物的合成与晶体结构

利用水热合成方法合成了2个新的双核稀土-异烟酸配合物修饰的Dawson型有机-无机杂化化合物[Ln2(HINC)4(H2O)8(P2W18O62)]·nH2O(Ln=Ce(1),Eu(2);n=16(1),9(2);INC=4-吡啶羧酸/异烟酸).化合物1与2同构,并通过红外光谱、元素分析和X-射线单晶衍射方法确定了该化合物的晶体结构.单晶结构分析表明化合物1属于三斜晶系,P-1空间群,晶胞参数a=1.323 6(3)nm,b=1.865 0(4)nm,c=2.287 2(5)nm,α=67.26(3)°,β=78.01(3)°,γ=70.34(3)°,V=4.883 8(17)nm3,Z=2.化合物2也属于三斜晶系,P-1空间群,晶胞参数a=1.320 1(2)nm,b=1.856 9(3)nm,c=2.285 6(4)nm,α=67.378(2)°,β=77.745(3)°,γ=70.039(3)°,V=4.839 8(13)nm3,Z=2.     

对咪唑基苯甲酸镉(Ⅱ)配合物的合成及结构研究

利用水热法合成了2个新的对咪唑基苯甲酸镉配合物Cd(C10N2O2H7)2·H2O(1)和Cd2(H2O)5(C10N2O2H7)(C9O6H3)·4H2O(2),通过元素分析、红外光谱和X-射线单晶衍射进行了表征.结果表明:化合物1属于正交晶系,Pnna空间群,a=1.389 5(5)nm,b=1.665 4(5)nm,c=0.828 2(5)nm,V=1.916 5(15)nm3,Z=4,R1=0.026 3,wR2=0.0793;化合物2属于单斜晶系,P21/c空间群,晶胞参数a=1.370 2nm,b=1.751 1nm,c=1.255 7(4)nm,β=114.819(6)°,V=2.734 6(14)nm3,Z=4,R1=0.057 3,wR2=0.166 7.     

芳醛缩N-(2-乙胺)-9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺Schiff碱衍生物的合成及晶体结构

合成了2个N-(2-乙胺)-9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺希夫碱衍生物,利用单晶X-射线衍射法测定了它们的晶体结构.化合物1为正交晶系,Pca21空间群,晶胞参数a=1.132 59(15)nm,b=2.535 6(4)nm,c=0.835 82(12)nm;α=90.00°,β=90.00°,γ=90.00°,V=2.4003(6)nm3,Z=4;化合物2为三斜晶系,P-1空间群,晶胞参数a=1.012 9(15)nm,b=1.190 1(16)nm,c=1.307 5(18)nm;α=67.17(3)°,β=72.88(3)°,γ=75.41(3)°,V=1.371(3)nm3,Z=2.     

二价镉配合物的合成与表征

由硝酸镉和2,3-吡嗪二羧酸(简称pdc)水热反应,得到无色透明针状单晶.经X射线单晶衍射法测定了该晶体的分子结构,其组成为[Cd(C6H2N2O4)]n或[Cd(pdc)]n.晶体学数据为:三斜晶系,P21/c空间群.a=1.072 8(6)nm,b=0.773 1(5)nm,c=0.867 4(5)nm,β=110.068(5)°,Z=4,μ=3.21 mm-1,R1=0.023,wR2=0.054.该化合物通过2个CdⅡ与pdc中的氧原子配位,形成一个新颖的二维结构.     

金属硫族化合物[Ni(en)3](Hen)SbSe4,[Sb(en)3]In3Te7的溶剂热生长及晶体结构

以溶剂热生长技术(Solvothermal technique)在180 C下以氯化物与具有氧化性的M 2Q(M=K,Rb;Q=Te,Se)反应,制备出新的硫族化合物[Ni(en)3](Hen)SbSe4(1),[Sb(en)3]In3Te7(2).化合物1的阳离子基团为过渡金属Ni与乙二胺(en)的配合物[Ni(en)3]2+及质子化的[Hen]+阳离子,阴离子基团为具有分立结构的[SbSe4]3-.化合物2的阳离子基团为[Sb(en)3]3+,阴离子基团为具有二维结构的2∞[In3Te7]3-.单晶X射线衍射结果表明,晶体1属三斜晶系,P1空间群,晶胞数据a=0.881 43(18)nm,b=0.962 35(19)nm,c=1.427 8(3)nm,α=104.74(3)°,β=92.47(3)°,γ=109.55(3)°,V=1.092 7(4)nm3,Z=2.晶体2属单斜晶系,P21/c空间群,晶胞数据:a=1.069 1(2)nm,b=1.693 2(3)nm,c=1.515 2(3)nm,α=90°,β=94.86(3)°,γ=90°.V=2.732 8(9)nm3,Z=4.     

Synthesis and characterization of quaternary chalcogenides InSn2Bi3Se8 and In0.2Sn6Bi1.8Se9

Quaternary chalcogenides InSn₂Bi₃Se₈ and In_0.2Sn₆Bi_1.8Se₉ were synthesized on direct combination of their elements in stoichiometric ratios at T>800 °C under vacuum. Their structures were determined with X-ray diffraction of single crystals. InSn₂Bi₃Se₈ crystallizes in monoclinic space group C2/m (No. 12) with a=13.557(3) Å, b=4.1299(8) Å, c=15.252(3) Å, β=115.73(3)°, V=769.3(3) Å³, Z=2, and R₁/wR₂/GOF=0.0206/0.0497/1.092; In_0.2Sn₆Bi_1.8Se₉ crystallizes in orthorhombic space group Cmc2₁ (No. 36) with a=4.1810(8) Å, b=13.799(3) Å, c=31.953(6) Å, V=1843.4(6) Å³, Z=4, and R₁/wR₂/GOF=0.0966/0.2327/1.12. InSn₂Bi₃Se₈ and In_0.2Sn₆Bi_1.8Se₉ are isostructural with CuBi₅S₈ and Bi₂Pb₆S₉ phases, respectively. The structures of InSn₂Bi₃Se₈ and In_0.2Sn₆Bi_1.8Se₉ feature a three-dimensional framework containing slabs of NaCl-(311) type with varied thicknesses. Calculations of the electronic structure and measurements of electrical conductivity indicate that these materials are semiconductors with narrow band gaps. Both compounds show n-type semiconducting properties with Seebeck coefficients −270 and −230 μV/K at 300 K for InSn₂Bi₃Se₈ and In_0.2Sn₆Bi_1.8Se₉, respectively.     

Investigating the Thermolysis Products of [Cd10Se4(SePh)12(P n Pr3)4] – The New Cluster Ion [Cd17Se4(SePh)28]2?

Analytical studies on the thermolysis products from [Cd₁₀Se₄(SePh)₁₂(PnPr₃)₄] are reported leading to the identification of the doubly negatively charged species [Cd₁₇Se₄(SePh)₂₈]²⁻. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) has been successfully applied to analyse the composition of a polycrystalline precipitate after treatment with SePh⁻ in tetrahydrofuran (THF). Presumably, SePh⁻ reacts with the insoluble (polymeric) cluster product as a charging ligand leading to dissolved monomeric units of the cluster anion [Cd₁₇Se₄(SePh)₂₈]²⁻. This cluster anion could also be crystallized from solutions as [Na(thf)₂18-crown-6][Cd₁₇Se₄(SePh)₂₈] and [Na(dme)₃]₂[Cd₁₇Se₄(SePh)₂₈]. The experimental results promise a wider applicability of the charged ligand exchange method for the electrospray mass spectrometric characterization of neutral clusters and to obtain intensive monodisperse cluster ion beams for further gas-phase studies. Dedicated to Prof. Dieter Fenske on the occasion of his 65th birthday.     

一个新颖的二重互穿的三维无机-有机杂化化合物[Cd(C5H3N2O2)2(H2O)]n的合成和晶体结构

近年来,由于无机-有机杂化化合物表现出独特的结构多样性以及在催化、光化学、电学和磁学等方面的巨大潜在应用.而引起了科学家们的广泛关注[1-4].     

Crystal and electronic structure of the red semiconductor Ba4LaSbGe3Se13 comprising the complex anion [Ge2Se7-Sb2Se4-Ge2Se7]

Ba₄LaGe₃SbSe₁₃ was prepared by reacting the elements under exclusion of air at 700°C, followed by slow cooling to room temperature. It crystallizes in a new type of the monoclinic space group P2₁/c, with lattice dimensions of a=1633.30(9) pm, b=1251.15(7) pm, c=1303.21(7) pm, β=103.457(2)°, V=2590.0(2) 10⁶ pm³ (Z=4). The structure contains isolated GeSe₄ as well as Ge₂Se₇ digermanate units. Two of the latter are interconnected via an Sb₂Se₄ bridge yielding an almost linear complex anion [Ge₂Se₇-Sb₂Se₄-Ge₂Se₇]¹⁴⁻. The oxidation states are assigned to be Ba^II, La^III, Ge^IV, Sb^III, and Se^−II, in accord with an electronically saturated nonmetal. The lone pair of Sb^III reflects itself in highly irregular Se coordination. The red color of the material is indicative of semiconducting behavior with an activation energy of 2.0 eV. Electronic structure calculations based on the LMTO approximation point to a smaller gap, typical for this calculation method. We utilized the COHP tool to explore the bonding character of the different Sb-Se interactions.     

Synthesis, structure, and magnetic and electronic properties of Cs2Hg2USe5

The compound Cs₂Hg₂USe₅ was obtained from the solid-state reaction of U, HgSe, Cs₂Se₃, Se, and CsI at 1123 K. This material crystallizes in a new structure type in space group P2/n of the monoclinic system with a cell of dimensions a=10.276(6) Å, b=4.299(2) Å, c=15.432(9) Å, β=101.857(6) Å, and V=667.2(6) Å³. The structure contains layers separated by Cs atoms. Within the layers are distorted HgSe₄ tetrahedra and regular USe₆ octahedra. In the temperature range of 25-300 K Cs₂Hg₂USe₅ displays Curie-Weiss paramagnetism with μ_eff=3.71(2) μ_B. The compound exhibits semiconducting behavior in the [010] direction; the conductivity at 298 K is 3×10⁻³ S/cm. Formal oxidation states of Cs/Hg/U/Se may be assigned as +1/+2/+4/− 2, respectively.     

Synthesis and characterization of quaternary selenides Sn2Pb5Bi4Se13 and Sn8.65Pb0.35Bi4Se15

Quaternary selenides Sn₂Pb₅Bi₄Se₁₃ and Sn_8.65Pb_0.35Bi₄Se₁₅ were synthesized from the elements in sealed silica tubes; their crystal structures were determined by single-crystal and powder X-ray diffraction. Both compounds crystallize in monoclinic space group C2/m (No.12), with lattice parameters of Sn₂Pb₅Bi₄Se₁₃: a = 14.001(6) Å, b = 4.234(2) Å, c = 23.471(8) Å, V = 1376.2(1) Å³, R₁/wR₂ = 0.0584/0.1477, and GOF = 1.023; Sn_8.65Pb_0.35Bi₄Se₁₅: a = 13.872(3) Å, b = 4.2021(8) (4) Å, c = 26.855(5) Å, V = 1557.1(5) Å³, R₁/wR₂ = 0.0506/0.1227, and GOF = 1.425. These compounds exhibit tropochemical cell-twinning of NaCl-type structures with lillianite homologous series L(4, 5) and L(4, 7) for Sn₂Pb₅Bi₄Se₁₃ and Sn_8.65Pb_0.35Bi₄Se₁₅, respectively. Measurements of electrical conductivity indicate that these materials are semiconductors with narrow band gaps; Sn₂Pb₅Bi₄Se₁₃ is n-type, whereas Sn_8.65Pb_0.35Bi₄Se₁₅ is a p-type semiconductor with Seebeck coefficients −80(5) and 178(7) μV/K at 300 K, respectively.     

The effects of doping ferromagnetic spinel CdCr2Se4 with Sb ions

Semiconducting spinel CdCr₂Se₄ orders ferromagnetically below T_C=130 K. A series of single-crystals of CdCr₂Se₄ doped with Sb³⁺ ions has been synthesized in order to study an effect of the substitution on the cation distribution and the magnetic properties. The compounds of Cd_ySb_xCr_zSe₄ have been investigated by means of X-ray diffraction, magnetization measurements and electron spin resonance spectroscopy. Two selected samples of the composition (Cd_1−xSb_x)[Cr₂]Se₄ with x=0.13 and 0.44 retained cubic symmetry with space group . The unit cell parameter appeared to be sensitive to the concentration of Sb³⁺ admixture: it increases with x, despite a close similarity in the ionic radii of Cd²⁺ and Sb³⁺ in tetrahedral coordination. Upon partial substitution of Cd²⁺ by Sb³ no obvious change in the Curie temperature was observed, however, the effective magnetic moment slightly increased, what may result from the appearance of Cr²⁺ ions. The characteristic feature of the system studied is an extended range of short-range magnetic order, in which the magnetic properties in the paramagnetic state are governed by the formation of ferromagnetic clusters, as indicated by both the bulk magnetometric and spectroscopic data.     

New tantalum polychalcogenides with infinite anionic chains: K12Ta6Se35 and KTaTe3

The new compounds K₁₂Ta₆Se₃₅ and KTaTe₃ have been synthesized through the reaction of Ta metal with a K₂Q_n(Q = Se, Te) flux. K₁₂Ta₆Se₃₅, crystallizes with 4 formula units in space group Pbcn of the orthorhombic system in a cell of dimensions a = 8.3390(17) Å, b = 13.259(3) Å, c = 56.023(11) Å (t = −120 °C). KTaTe₃ crystallizes with 20 formula units (or 4 formula units of K₅Ta₅Te₁₅) in the monoclinic space group P2₁/c in a cell of dimension a = 7.7177(15) Å, b= 13.826(3) Å, c = 30.981(6) Å, and β = 90.11(3)° (t = −120 °C). Each structure consists of infinite anionic chains of Ta-containing polyhedra well separated by K⁺ cations. In K₁₂Ta₆Se₃₅ there are Ta₂Se₁₁ units formed by the face sharing of two TaSe₇ elongated bipyramids. These Ta₂Se₁₁ units are in turn interconnected by Se₂ and Se₃ units to form _α¹[Ta₆Se₃Se₃₅¹²⁻]infinite chains. In KTaTe₃, the _α¹[TaTe₃⁻] infinite chains arise from the face sharing of distorted TaTe₆ octahedra.     

Rb2BaNb2Se11: A new quaternary niobium polyselenide with infinite anionic chains composed of Nb2Se11 building block

The quaternary compound Rb₂BaNb₂Se₁₁ has been synthesized by reacting Nb metal with an in situ formed flux of Rb₂Se₃, BaSe and Se at 773 K. Rb₂BaNb₂Se₁₁ crystallizes in the monoclinic space group P2₁/c with four formula units and lattice parameters a=7.8438(5) Å, b=13.6959(6) Å, c=17.0677(13) Å, β=97.917(9)°. The structure consists of one-dimensional anionic chains formed by interconnection of dimeric [Nb₂Se₁₁] units. The chains are directed along the crystallographic c-axis with Rb⁺ and Ba²⁺ ions being located between the chains. The [Nb₂Se₁₁] units are formed by face sharing of two NbSe₇ bipyramids and are joined by Se₂²⁻ dianions to form infinite ¹_∞[Nb₂Se₁₁⁴⁻] chains. The compound was characterized with infrared spectroscopy in the FIR region, Raman and UV/Vis diffuse reflectance spectroscopy.     

New Selenidogermanates with Transition-Metal Complexes as Counterions: Solvothermal Synthesis, Crystal Structures, and Properties of [Mn(en)3]2Ge2Se6 and [Fe(dien)2]2Ge2Se6

Summary. New selenidogermanates [Mn(en)₃]₂Ge₂Se₆ (en = ethylenediamine) and [Fe(dien)₂]₂Ge₂Se₆ (dien= diethylenetriamine) were synthesized by the reaction of germanium dioxide, elemental selenium, and transition metal chlorides in respectively en and dien. Both compounds crystallize in the monoclinic space group P2₁/n with two formula units in the unit cell, and consist of discrete [Ge₂Se₆]⁴⁻ anions with transition metal complex cations as counter ions. The [Ge₂Se₆]⁴⁻ anion is formed by two GeSe₄ tetrahedra sharing a common edge to form a planar Ge₂Se₂ four-membered ring. The [Mn(en)₃]²⁺ and [Ni(dien)₂]²⁺ complex cations are in distorted octahedral geometry. In both selenidogermanates extensive N–H···Se hydrogen bonding contacts lead to 3-dimensional network structures. The band gaps of 2.36 and 2.25 eV were derived from optical absorption spectra. Thermogravimetric analysis shows that the first compound decomposes in two steps under the nitrogen stream, while the second exhibits a one-step decomposition process.