Synthesis,Crystal Structures,and Optical Properties of New Quaternary Metal Chalcogenides of Group 5: Cs2AgVS4, K2AgVSe4, Rb2AgVSe4, Rb2AgNbS4, and Cs2AgNbSe4

The new quaternary compounds Cs₂AgVS₄, K₂AgVSe₄, Rb₂AgVSe₄, Rb₂AgNbS₄, and Cs₂AgNbSe₄ were prepared using the reactive flux method. In this structure type infinite chains of edge-sharing AgQ₄- and M^VQ₄-tetrahedra are running parallel to the crystallographic a-axis. The chains are separated by alkali cations. A linear relationship between the size of the alkali cation A⁺ and the Q–Q interchain distances was found. These compounds are isostructural with the analogous quaternary copper chalcogenides. The optical properties were studied by collecting UV/Vis transmission and reflectance spectra which allowed to derive the optical band gaps. The colours of the vanadium compounds range from black to dark violet with optical band gaps between 1.7 and 1.8 eV. In addition, the behaviour of the samples was studied using polarized light. Under these experimental conditions the niobium compound Rb₂AgNbS₄ changes its colour from green to red when the direction of the polarization plane is changed by 90°.     

Synthesis and Single Crystal Structure of RbEr_2Cu_3Se_5

1 INTRODUCTION Halide fluxes are excellent media for growing single crystals of chalcogenides[1~3]. It is well known that during the single crystal growth via flux methods, occasional inclusion of the flux elements in the structure leads to the formation of new phases[4~9]. Several rare earth chalcogenides have been prepared through such reactive halid flux methods[4~9]. Thus we used RbCl as reactive flux to explore a new quaternary selenide by the reaction of ErCuSe precursor with Rb…     

Synthesis and Crystal Structure of Ho_4S_3Si_2O_7

1 INTRODUCTION Halide fluxes are excellent media for growing single crystals of chalcogenides[1~5]. On our research in the Ln-Cu-Zn-Se system to find new phases and to search for potential infrared ceramic materials, two new compounds, KHo2CuSe4 and KEr2CuSe4, were synthesized from the reaction of the precursor with KCl flux[6]. In an attempt to synthesize the homologous sulfide by the same method using KBr as flux in a sealed evacuated quartz tube, single crystals of Ho4S3Si2O7 w…     

Synthesis and Crystal Structure of a Heterometallic Trinuclear Ni/Ag/S Compound

A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni(II) atom and the two silver(I) atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni(edt)2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581(11),b = 12.239(9),c = 22.316(17) ,β = 103.08(2)o,V = 3613(5) 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F(000) = 1604,T = 293(2) K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I > 2σ(I).     

K2CdSnS4的溶剂热合成与晶体结构

利用溶剂热法合成了层状硫代锡(Ⅲ)酸镉(Ⅱ)化合物K₂CdSnS₄。单晶X-射线衍射分析结果表明,化合物属单斜晶系,C2/c空间群,a=1.1021(5)nm,b=1.1030(5)nm,c=1.5151(10)nm,α=90°,β=100.416(12)°,γ=90°,V=1.8114(17)nm³,Z=8,D_c=3.209g·cm^-3,M_r=437.60,μ=6.853mm^-1,F(000)=1600,λ=0.071073nm,R=0.1042,wR=0.2008。该化合物由类金刚烷[Cd₂Sn₂S₁₀]^8-结构单元互相连接形成层状结构。紫外-可见漫反射光谱研究表明,化合物为半导体,带隙为2.2eV。     

K_2CdSnS_4的溶剂热合成与晶体结构(英文)

利用溶剂热法合成了层状硫代锡(Ⅲ)酸镉(Ⅱ)化合物K2CdSnS4。单晶X-射线衍射分析结果表明,化合物属单斜晶系,C2/c空间群,a=1.102 1(5)nm,b=1.103 0(5)nm,c=1.515 1(10)nm,α=90°,β=100.416(12)°,γ=90°,V=1.811 4(17)nm3,Z=8,Dc=3.209 g·cm-3,Mr=437.60,μ=6.853 mm-1,F(000)=1 600,λ=0.071 073 nm,R=0.104 2,wR=0.200 8。该化合物由类金刚烷[Cd2Sn2S10]8-结构单元互相连接形成层状结构。紫外-可见漫反射光谱研究表明,化合物为半导体,带隙为2.2 eV。     

配合物[Ln(CH3COO)2(NO3)(bipy)]2的合成与晶体结构

合成了５种新型镧系四元混合阴离子配合物,用Ｘ射线四圆衍射仪测定了［Ｐｒ（ＣＨ３ＣＯＯ）２（ＮＯ３）（ｂｉｐｙ）］２的晶体结构,四个醋酸根呈两种配位方式,测定了铕和钆配合物的荧光和ＥＳＲ谱．     

Synthesis,Crystal Structure,and NLO Property of the Chiral Sulfide Sm4InSbS9

The chiral sulfide Sm₄InSbS₉ was prepared from a stoichiometric mixture of the elements at 1223 K in an evacuated silica tube. It crystallizes in the chiral tetragonal space group P4₃2₁2 with a = 10.0042(4) Å, c = 27.6810(15) Å, V = 2770.4(2) ų, and Z = 8. The structure features infinite helical chains of [In₂Sb₂S₁₁^10–]_∞ propagating along the c direction that are separated by Sm³⁺ cations and S^2– anions. It shows the second harmonic generation with an intensity of 0.75 times that of benchmark AgGaS₂ at 2.05 µm laser in type I phase matchable behavior. UV/Vis diffuse reflectance spectroscopy study shows its optical gap of around 2.13 eV.     

Synthesis and Crystal Structure of a New Alkali Metal Tantalum Sulfide: Na3TaS4

Needle-shaped, moisture sensitive, yellow crystals of Na₃TaS₄ were obtained by the reaction of Na₂S₃, Ta, and S at 450 °C. The structure was determined by single crystal X-ray diffraction and refined to R1 and wR2 values of 0.0172 and 0.0381, respectively. Na₃TaS₄ crystallizes with 32 formula units in the orthorhombic space group Fdd2 (No.: 43) with a = 27.113(4), b = 28.326(6) and c = 7.918(1) Å. The structure consists of discrete tetrahedral TaS₄^3– ions and Na⁺ ions.     

Synthesis and Crystal Structure of 4-Arylamino-6-chloropyrido[3,2-d]pyrimidine

The title compounds 4a～c were synthesized and characterized by IR,NMR and MS.The crystal structure of C16H13ClN4O2·HBr·H2O(I),the quaternary ammonium salt of 4c,was determined by X-ray diffraction analysis.I crystallizes in triclinic,space group P1 with a = 8.3121(8),b = 9.3885(8),c = 13.2903(12),α = 106.788(2),β = 95.204(3),γ = 110.871(2)o,V = 905.81(14)3,Z = 2,C16H16BrClN4O3,Mr = 427.68,Dc = 1.568 g/cm3,F(000) = 432.00,μ = 2.446 mm-1,R = 0.0496 and wR = 0.127.X-ray analysis reveals that C(15) in the BrCH2COOH molecule binds to the N(1) of pyrimidine ring to form the quaternary ammonium salt.Two adjacent I molecules are connected by hydrogen bonds through carboxylate oxygen,water molecule and hydrobromic acid.     

以有机溶剂热生长技术制备金属硫族化合物[Mn(en)_3]PdSe_2及其晶体结构分析

以有机溶剂热生长技术 (solvothermaltechnique) ,即在 180℃乙二胺 (en)溶液中 ,以MnCl3,PdCl2 ,K2 Se在密闭容器中反应 7d ,制备出新的硫族化合物 [Mn(en) 3]PdSe2 ,其阴离子基团为 [PdSe2 ]2 -,阳离子基团为过渡金属Mn与乙二胺 (en)的配合物 :[Mn(en) 3]2 +.以单晶X射线衍射技术解得该晶体结构属正交晶系 ,空间群为Pbcn ,[Mn(en) 3]·PdSe2 (Ⅰ )的晶胞数据 :a =1.1484( 2 ) ,b=1.5 0 5 7( 3 ) ,c =0 .93 62 2 ( 19)nm ,Z =4.     

Synthesis and Structure of ThTe2I2

The new ternary compound ThTe₂I₂, which crystallizes in the NbS₂Cl₂ structure type, was prepared from the elements and characterized by single‐crystal X‐ray diffraction. It adopts a monoclinic layer structure where binuclear [Th₂(Te₂)₂]⁴⁺ units with square‐antiprismatically coordinated thorium are linked together by I^– anions to form sheets parallel to the (001) plane. The space group is C2/m and the lattice constants are a = 7.642(1) Å, b = 14.336(4) Å, c = 7.727(2) Å, and β = 111.27(2)° for Z = 4. The final R1/wR2 for the crystal structure refinement was 0.029/0.073.     

含过渡金属镉或汞的四元硫化物的溶剂热合成及性能

利用溶剂热法合成了2种四元硫化物Rb₂CdSbS₃（SH）（1）和Rb₂HgSb₄S₈（2）。单晶X射线衍射分析表明,化合物1为一维链状结构,由[CdSbS₃（SH）]^2-阴离子和Rb⁺阳离子组成。化合物2为二维层状结构,由[HgSb₄S₈]^2-阴离子和Rb⁺阳离子组成。固体紫外可见漫反射光谱分析结果表明,化合物1和2的带隙分别为2.06和2.15 eV。荧光分析结果表明化合物1和2均具有黄光发射特性。     

层状硼酸铍H2BeB4O8的合成与结构

在硼酸介质中合成了一种新的具有层状结构的多硼酸铍H₂BeB₄O₈,并利用多晶X射线衍射方法确定了晶体结构。H₂BeB₄O₈的空间群为P2₁/n,晶胞参数a=17.7564(2)?,b=4.2948(1)?,c=7.1532(1)?,β=96.8797(9)°。H₂BeB₄O₈的层状结构由双三元环[BeB₄O₁₁]构成,层之间通过垂直于层平面的羟基所形成的氢键连接成三维结构。     

Synthesis, Single-crystal Structure, and Optical and Magnetic Properties of CaEr2S4

Brown needle-like crystals of CaEr2S4 were isolated as the major product from a reaction of elements and binary sulfides by a two-step flux technique. CaEr2S4 crystallizes in the orthorhombic space group Pnma with a = 12.845(4), b = 3.862(4), c = 13.001(2) , V = 645.0(7) 3, Z = 4, F(000) = 880, μ(MoKα) = 27.794 mm-1, the final R = 0.0528 and wR = 0.0562 for 1070 observed reflections with I > 3σ(I). The CaEr2S4 structure forms a three-dimensional framework that consists of interconnected tetra-octahedral Er4S18 fragments. Ca2+ cations, in a monocapped trigonal prism geometry, are stuffed in two parallel rows into the one-dimensional channels along the b direction. CaEr2S4 is an infrared-transparent semiconductor with a band gap of 1.81 eV. Magnetic susceptibility measurements over 6～300 K indicate a Curie-Weiss paramagnetic behavior for the phase, with an effective magnetic moment of 9.64(1) μB per Er3+ ion.     

Synthesis,Crystal and Electronic Structure,and Optical Property of the Quaternary Selenide: La3Sb0.33SiSe7

The quaternary selenide, La₃Sb_0.33SiSe₇, was prepared from stoichiometric mixtures of elements by solid‐state reactions at 1223 K in an evacuated silica tube. La₃Sb_0.33SiSe₇ crystallizes in the chiral P6₃ space group and belongs to the Ce₃Al_1.67S₇ structure type. Its structure features one‐dimensional chains of face‐sharing SbSe₆ octahedra running parallel to the c direction surrounded by the discrete SiSe₄ tetrahedra and La cations. UV/Vis/NIR diffuse reflectance spectroscopy study shows its optical gap of around 1.75 eV. DFT study indicates an indirect bandgap with an electronic transfer excitation from Se 4p to La 5d orbital electrons.     

Ba2In2Q5 (Q = S,Se): Synthesis,Crystal Structures,Electronic Structures,and Optical Properties

Two ternary metal chalcogenides, Ba₂In₂Q₅ (Q = S, Se) were successfully synthesized by solid‐state reactions. They are isostructural and crystallize in the orthorhombic space group Pbca (no. 61). Both of them have a similar three‐dimensional (3D) framework structure, which is composed of [InQ₄] (Q = S, Se) tetrahedra that are alternatingly connected on layer in the ab plane, with Ba²⁺ cations arranged between In–S or In–Se layers for electric charge balance. The measured Raman and IR spectra show that title compounds have broad transparency range up to 20 μm. From the UV/Vis/NIR diffuse reflectance spectra, it can be seen that the bandgaps of Ba₂In₂S₅ and Ba₂In₂S₅ are 2.47 eV and 2.12 eV, which are larger than these of the calculation values (Ba₂In₂S₅, 2.362 eV and Ba₂In₂Se₅, 1.908 eV), respectively. The calculated partial densities of states indicate that the bandgaps are determined by the interaction of S‐3p and In‐5s (Ba₂In₂S₅) or Se‐4p and In‐5s (Ba₂In₂Se₅), respectively. The calculated birefringences (Δn) are about 0.03 (Ba₂In₂S₅) and 0.05 (Ba₂In₂Se₅) as the wavelength above 1 μm, respectively.     

簇合物[Et4N]2[Mo2S4(SCH2CH2S)2]的合成及晶体结构

以(NH4)2MoS4,Et4NBr,HSCH2CH2SH为原料合成了新的簇合物——[Et4N]2[Mo2S4(SCH2CH2S)2],其结构经X射线四圆衍射仪,IR。UV及元素分析确证。其晶体属单斜晶系。晶胞参数为：a=1．0304(8)nm,b=1．4158(8)sin。c=1．1417(1)nm,V=1．63801nm^3,z=4。晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0．084。     

NaKV_2O_6的水热合成与结构

以水热法合成偏钒酸的复盐ＮａＫＶ２Ｏ６并测定晶体结构。ＮａＫＶ２Ｏ６晶体属单斜晶系，Ｃ２空间群，ａ＝１０．５６８（３），ｂ＝１０．０８２（２），ｃ＝５．８１０（２）Ａ，β＝１０３．８７（２）°，Ｖ＝６０１．０（３）Ａ３，Ｍｒ＝２５９．９７，Ｆ（０００）＝４９６，μ＝３７．３８ｃｍ（－１），Ｚ＝４，Ｄｃ＝２．８７ｇ·ｃｍ－３，Ｄｏ＝２．８５ｇ·ｃｍ（－３）。结构由重原子法解出，全矩阵最小二乘法修正至Ｒ＝０．０２９，Ｒω＝０．０４３。无水偏钒酸盐骨架为链状结构，其阴离子骨架由ＶＯ４四面体共顶点氧形成ＶＯ－３无限链，链间为平衡电荷的阳离子，阳离子与链之间靠静电引力结合在一起。