[(enH)2(enH2)Sn2Se6]的合成、结构及性能研究

采用溶剂热法,以K2Se:SnCl2·2H2O∶Se∶en=1∶1∶4∶48的摩尔比,在150 ℃下反应5d,生成黄色透明柱状晶体[(enH2)2Sn2Se6·en]。该晶体属于三斜晶系 ,空间群为Pl^-,晶胞参数,a=0.8659(2)nm,b=1.1055(2)nm,c=0.66360(10)nm, a=104.44(3)°,β=110.93(3)°,γ=79.74(3)°,V=0.57198(19)nm^3,Z=1.[ (enH2)Sn2Se6]晶体由质子化的乙二胺正离子（enH)^+,(enH2)^2+和二聚硒代锡根 负离子（Sn2Se6)^4-堆积而成。在AxSn2Se6系列化合物,正离子A的大小对晶体结 构的类型产生重要的影响。研究表明,此晶体具有1.76eV的能隙（Eg）,是个半导 体,对太阳辐射具有选择吸收特性,在温度低于180℃时是稳定的。     

[(enH)_2(enH_2)Sn_2Se_6]的合成、结构及性能研究

采用溶剂热法 ,以K2 Se∶SnCl2 ·2H2 O∶Se∶en =1∶1∶4∶48的摩尔比 ,在 15 0℃下反应 5d ,生成黄色透明柱状晶体[(enH2 ) 2 Sn2 Se6·en] .该晶体属于三斜晶系 ,空间群为P 1,晶胞参数 ,a =0 865 9( 2 )nm ,b =1 10 5 5 ( 2 )nm ,c =0 663 60 ( 10 )nm ,α =10 4 44 ( 3 )° ,β =110 93 ( 3 )° ,γ =79 74( 3 )° ,V =0 5 7198( 19)nm3 ,Z =1.[(enH) 2 (enH2 )Sn2 Se6]晶体由质子化的乙二胺正离子 (enH) + ,(enH2 ) 2 + 和二聚硒代锡酸根负离子 (Sn2 Se6) 4 -堆积而成 .在AxSn2 Se6系列化合物 ,正离子A的大小对晶体结构的类型产生重要的影响 .研究表明 ,此晶体具有 1 76eV的能隙 (Eg) ,是个半导体 ,对太阳辐射具有选择吸收特性 ,在温度低于 180℃时是稳定的 .     

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.     

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MnCl~3,PdCl~2,K~2Se在密闭容器中反应7d,制备出新的硫族化合物[Mn(en)~3]PdSe~2,其阴离子基团为[PdSe~2]^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]PdSe~2(Ⅰ)的晶胞数据：a=1.1484(2),b=1.5057(3),c=0.93622(19)nm,Z=4。     

Solvothermal Synthesis,Crystal Structure and Optical Property of Lanthanide Selenidostannate [{Tb（en）_3}_2（μ-OH）_2]Sn_2Se_6 with a 3-D H-bonded Network

An inorganic-organic hybrid lanthanide selenidostannate [{Tb(en)3}2(μ-OH)2]Sn2Se6(1) was synthesized by the solvothermal method.1 crystallizes in the monoclinic system,space group P21/n with a=10.120(2),b=11.781(3),c=15.403(3),β=99.534(5)°,V=1811.1(7)3,Mr=1423.62,Z=2,Dc=2.611 g/cm3,μ=11.281 mm-1,F(000)=1312,S=1.101,the final R= 0.0400 and wR=0.0853 for 3242 observed reflections with Ⅰ> 2σ(Ⅰ).1 consists of a [Sn2Se6]4-and a [{Tb(en)3}2(μ-OH)2]4+ ions.The [Sn2Se6]4-anion is constructed by two SnSe4 tetrahedra sharing a common edge.The binuclear [{Tb(en)3}2(μ-OH)2]4+ complex is composed of two [Tb(en)3]3+ ions joined by two μ-OH bridging ligands.The Tb3+ ion lies in an eight-coordinated bicapped trigonal prism.In 1,the [Sn2Se6]4-and [{Tb(en)3}2(μ-OH)2]4+ moieties are connected into a 3-D network via N-H···Se and O-H···Se H-bonds.     

无机-有机杂化硫属化合物[Mn(1,2-dap)_2(H_2O)]_2(μ-Sn_2Q_6)(Q=S、Se)和[Mn(tren)]_2(μ-Sn_2S_6)的合成、晶体结构与性能（英文）

采用溶剂热方法合成了3个多元硫属化合物[Mn(1,2-dap)2(H2O)]2(μ-Sn2Q6)(Q=S(1)和Se(2))和[Mn(tren)]2(μ-Sn2S6)(3),用X-射线单晶衍射测定了化合物的结构,并通过红外光谱、紫外-可见漫反射光谱对其进行了表征。单晶结构解析表明,化合物1和2都属于正交晶系,Pccn空间群(No.56),晶体结构是由[Mn(1,2-dap)2(H2O)]2+配合物阳离子和[Sn2Q6]4-二聚体通过Mn-Q键连接而成的[Mn(1,2-dap)2(H2O)]2(μ-Sn2Q6)低聚体,相邻的低聚体之间通过氢键相连形成三维结构。化合物3属于三斜晶系,晶体结构是由[Mn(tren)]2(μ-Sn2S6)单元通过氢键连接而成的二维结构。紫外-可见漫反射光谱结果显示化合物1,2和3的带隙分别为2.5,2.1,2.4 e V,属于半导体材料。     

无机-有机杂化硫属化合物[Mn(1,2-dap)2(H2O)]2(μ-Sn2Q6)(Q=S、Se)和[Mn(tren)]2(μ-Sn2S6)的合成、晶体 结构与性能

采用溶剂热方法合成了3个多元硫属化合物[Mn(1,2-dap)2(H2O)]2(μ-Sn2Q6)(Q=S(1)和Se(2))和[Mn(tren)]2(μ-Sn2S6)(3),用X-射线单晶衍射测定了化合物的结构,并通过红外光谱、紫外-可见漫反射光谱对其进行了表征。单晶结构解析表明,化合物1和2都属于正交晶系,Pccn空间群(No.56),晶体结构是由[Mn(1,2-dap)2(H2O)]2+配合物阳离子和[Sn2Q6]4-二聚体通过Mn-Q键连接而成的[Mn(1,2-dap)2(H2O)]2(μ-Sn2Q6)低聚体,相邻的低聚体之间通过氢键相连形成三维结构。化合物3属于三斜晶系,晶体结构是由[Mn(tren)]2(μ-Sn2S6)单元通过氢键连接而成的二维结构。紫外-可见漫反射光谱结果显示化合物1,2和3的带隙分别为2.5,2.1,2.4 e V,属于半导体材料。     

[M(dap)3]2(Sb2Se5)·xH2O(M=Ni,x=2;M=Zn,x=0)的溶剂热合成及晶体结构

利用溶剂热法合成了2种新的有机杂化锑硒化合物[Ni(dap)3]2(Sb2Se5)].2H2O(1)和[Zn(dap)3]2(Sb2Se5)](2)(dap=1,2-丙二胺),单晶X射线衍射分析结果表明,1属于三方晶系,P3121空间群,晶胞参数为a=10.7574(14),b=10.7574(14),c=31.672(4),γ=120.00°,z=4。2属于单斜晶系,P21空间群,晶胞参数为a=10.772(2),b=16.391(3),c=11.704(2),β=100.912(4)°,z=4。在2种化合物中,Ni2 与Zn2 离子分别与3个dap配体螯合形成畸变八面体几何构型,其中dap配体的N原子是无序的,而二聚[Sb2Se5]2-阴离子是由2个SbSe3三角锥共用1个Se原子连接而成。     

混合价硒代锡酸盐K2Sn2Se4的固相合成、晶体结构和反射光谱研究

采用反应性熔盐法在550℃下合成一种新型混合价硒代锡酸盐晶体(K2Sn2Se4).该晶体属于四方晶系,空间群为I4cm,晶胞参数a=0.81524(12)nm,b=0.81524(12)nm,c=0.67152(13)nm.K2Sn2Se4晶体具有一维链状结构,一维的1∞[Sn2Se4]2-链沿c轴方向无限扩展,K+插入链之间.K2Sn2Se4属于Zintl型化合物,具有半导体特性.漫反射光谱法研究结果表明,该化合物的光学能隙(Eg)为1.7eV.     

金属碲化物[Ga(en)~3]In~3Te~7晶体结构和性质的研究

以有机溶剂热生长技术(solvothermaltechnique),即在180℃乙二胺(en)溶液中,以GaCl~3,InCl~3,Rb~2Te和Te在密闭容器中反应7d,制备出新的硫族化合物[Ga(en)~3]In~3Te~7。其阴离子基团为Zintlanion:~∞^2[In~3Te~7]^3^-,阳离子基团为Ga与乙二胺(en)的配合物:[Ga(en)~3]^3^+。以单晶X射线衍射技术解得该晶体结构属单钭晶系,空间群为P2~1/c,(no.14),{Ga(en)~3]In~3Te~7的晶胞数据：a=1.0460(2)nm,b=1.6981(3)nm,c=1.4994(6)nm,α=90°,β=95.46(2)°,γ=90°,V=2.651(1)nm^3,Z=4。热分析结果表明,该化合物的热分解分三步进行。光学性质测试表明它们是半导体材料,禁带宽度为1.65eV。     

Straightforward route to the adamantane clusters [Sn4Q10]4- (Q = S, Se, Te) and use in the assembly of open-framework chalcogenides (Me4N)2M[Sn4Se10] (M = Mn(II), Fe(II), Co(II), Zn(II)) including the first telluride member (Me4N)2Mn[Ge4Te10

The reaction of K(2)Sn(2)Q(5) (Q = S, Se, Te) with stoichiometric amounts of alkyl-ammonium bromides R(4)NBr (R = methyl or ethyl) in ethylenediamine (en) afforded the corresponding salts (R(4)N)(4)[Sn(4)Q(10)] (Q = S, Se, Te) in high yield. Although the compound K(2)Sn(2)Te(5) is not known, this reaction is also applicable to solids with a nominal composition "K(2)Sn(2)Te(5)" which in the presence of R(4)NBr in en are quantitatively converted to the salts (R(4)N)(4)[Sn(4)Te(10)] on a multigram scale. These salts contain the molecular adamantane clusters [Sn(4)Q(10)](4-) and can serve as soluble precursors in simple metathesis reactions with transition metal salts to synthesize the large family of open-framework compounds (Me(4)N)(2)M[Sn(4)Se(10)] (M = Mn(2+), Fe(2+), Co(2+), Zn(2+)). Full structural characterization of these materials as well as their magnetic and optical properties is reported. Depending on the transition metal in (Me(4)N)(2)M[Sn(4)Se(10)], the energy band gaps of these compounds lie in the range of 1.27-2.23 eV. (Me(4)N)(2)Mn[Ge(4)Te(10)] is the first telluride analogue to be reported in this family. This material is a narrow band gap semiconductor with an optical absorption energy of 0.69 eV. Ab initio electronic band structure calculations validate the semiconductor nature of these chalcogenides and indicate a nearly direct band gap.     

Reactivity of chalcogenostannate compounds: syntheses,crystal structures,and electronic properties of novel compounds containing discrete ternary anions [MII4(mu4-Se)(SnSe4)4]10- (MII = Zn,Mn)

Reactions of K4[SnSe4].1.5MeOH with ZnCl2 or MnCl2.4H2O in water/methanol mixtures yield novel compounds [K10(H2O)16(MeOH)0.5][M4(mu4-Se)(SnSe4)4] (M = Zn, 2; Mn, 3) in high yields; 2 and 3 contain the first discrete ternary Zn/Sn/Se or Mn/Sn/Se cluster anions. Both compounds were unambiguously characterized by X-ray diffraction (tetragonal, space groups P43212 and P41212, respectively) revealing chiral anionic structures within chiral crystals. Optical spectra of 2 and 3 indicate energy differences for the lowest electronic excitations (Eg = 2.57 eV, 2; 2.27 eV, 3) that are very close to the band gap values observed for mesoporous solids with polymeric M/Sn/E networks. DFT investigations on the electronic situation and first ESR studies agree in that they demonstrate a high-spin ground state in the case of 3 with 20 unpaired electrons at four uncoupled MnII centers.     

一维链状冠醚配合物[K(B18-C-6)]_2[M(SCN)_4](M=Pd,Pt)的合成与结构

合成了苯并18-冠-6（B18-C-6）与K_2[Pd(SCN)_4]生成的配合物[K（B18-C-6 ）]_(12) [Pd(SCN)_4] (1), [K(B18-C-6)]_2[Pt(SCN)_4] (2)和[K(B18-C-6)]_2 [Pt(SCN)_4]·C_2H_4Cl_2 (3),并通过元素分析、红外光谱、单晶X射线衍射进行 了表征。1和2为单斜晶系,空间群P2_l/n,晶体学数据：1, a = 1.00970(17) nm, b = 1.3157(2) nm, c = 1.7303(3) nm, β = 94.841(2)°, V = 2.2852(7) nm~3, Z = 2, F(000) = 1136, R_1 = 0.0257。3为三斜晶系,空间群P1,晶体学 数据：a = 0.95914(18) nm, b = 1.2137(2) nm, c = 2313(2) nm, α = 63.693 (2)°, β = 76.293(2)°, γ-1.2406(4) n~3, Z = 1 F(000)618,R_1 = 0.0366 。在固态,三个配合物相邻的两个[K（B18-C-6）]~+基团通过冠醚氧化原子与钾的 子的相边接而形成一维链状结构。     

CRYSTAL STRUCTURES OF [Bu4N]2[M2Ag3（ μ3—S）2（μ—S）4S2Et2dtc]（M=W,Mo）

<正> The title compounds were prepared from the reation of (NH4)2MS4 (M=W,Mo),AgNO3,NadtcEt2 and Et4NBr in CH3CN-H2O solution. The isomorphous compounds [Bu4N]2[W2Ag3S8Et2du] ( I ) and [Bu4N]2[Mo2Ag3S8Et2dtc] (Ⅱ) crystallize in triclinic space qroup Pi with the following crystal parameters:α=13. 043(4),b = 21. 640(6),c=10. 757(6)A ,α=95. 09(5),β = 91. 90(4),γ = 98. 57(3)°,Z = 2,V = 2987A3,Dc=1. 76g/cm3 for I 5;a= 12. 989(2) ,b=21. 574 (9) ,c= 10. 7/1(1) A .α= 95. 06(7), β=91. 61(4), γ=98. 52(2)°, Z = 2,V = 2961 A3.Dc= 1. 58g/cm3 for Ⅱ . The final R and Rw values are 0. 061 and 0. 072 for Ⅰ ,and 0. 062 and 0. 076 for Ⅱ The M2Ag3 (M = W, Mo) unit in anion M2Ag3S8Et2dtc forms a five-membered ring.     

Rare-earth metal(III) oxide selenides M4O4Se[Se2] (M=La, Ce, Pr, Nd, Sm) with discrete diselenide units: crystal structures, magnetic frustration, and other properties

The rare-earth metal(III) oxide selenides of the formula La4O4Se[Se2], Ce4O4Se[Se2], Pr4O4Se[Se2], Nd4O4Se[Se2], and Sm4O4Se[Se2] were synthesized from a mixture of the elements with selenium dioxide as the oxygen source at 750 degrees C. Single crystal X-ray diffraction was used to determine their crystal structures. The isostructural compounds M4O4Se[Se2] (M=La, Ce, Pr, Nd, Sm) crystallize in the orthorhombic space group Amm2 with cell dimensions a=857.94(7), b=409.44(4), c=1316.49(8) pm for M=La; a=851.37(6), b=404.82(3), c=1296.83(9) pm for M=Ce; a=849.92(6), b=402.78(3), c=1292.57(9) pm for M=Pr; a=845.68(4), b=398.83(2), c=1282.45(7) pm for M=Nd; and a=840.08(5), b=394.04(3), c=1263.83(6) pm for M=Sm (Z=2). In their crystal structures, Se2- anions as well as [Se-Se]2- dumbbells interconnect {[M4O4]4+} infinity 2 layers. These layers are composed of three crystallographically different, distorted [OM4]10+ tetrahedra, which are linked via four common edges. The compounds exhibit strong Raman active modes at around 215 cm(-1), which can be assigned to the Se-Se stretching vibration. Optical band gaps for La4O4Se[Se2], Ce4O4Se[Se2], Pr4O4Se[Se2], Nd4O4Se[Se2], and Sm4O4Se[Se2] were derived from diffuse reflectance spectra. The energy values at which absorption takes place are typical for semiconducting materials. For the compounds M4O4Se[Se2] (M=La, Pr, Nd, Sm) the fundamental band gaps, caused by transitions from the valence band to the conduction band (VB-CB), lie around 1.9 eV, while for M=Ce an absorption edge occurs at around 1.7 eV, which can be assigned to f-d transitions of Ce3+. Magnetic susceptibility measurements of Ce4O4Se[Se2] and Nd4O4Se[Se2] show Curie-Weiss behavior above 150 K with derived experimental magnetic moments of 2.5 micro B/Ce and 3.7 micro B/Nd and Weiss constants of theta p=-64.9 K and theta p=-27.8 K for the cerium and neodymium compounds, respectively. Down to 1.8 K no long-range magnetic ordering could be detected. Thus, the large negative values for theta p indicate the presence of strong magnetic frustration within the compounds, which is due to the geometric arrangement of the magnetic sublattice in form of [OM4]10+ tetrahedra.     

Mixed-valent selenidoantimonates(III,V) with transition-metal complexes as counterions: solvothermal syntheses and characterization of [M(dien)2]2Sb4Se9 (M = Mn, Fe), [Co(dien)2]2Sb2Se6, and [Ni(dien)2]2Sb2Se5

Novel selenidoantimonate compounds [M(dien)2]2Sb4Se9 [M = Mn (1), Fe (2)], [Co(dien)2]2Sb2Se6 (3), and [Ni(dien)2]2Sb2Se5 (4) (dien = diethylenetriamine) were solvothermally synthesized and characterized. The unique features of compounds 1-3 are the mixed-valent anionic structures constructed by the Sb(III)Se3 trigonal pyramid and Sb(V)Se4 tetrahedron. Three Sb(III)Se3 pyramids share common corners, forming a heterocyclic Sb3Se6 moiety, and the Sb3Se6 moieties are further connected with Sb(V)Se4 tetrahedra to form the novel one-dimensional [Sb4Se9(4-)]n anionic chain in 1 and 2. The discrete [Sb2Se6]4- anion in 3 is formed by an Sb(III)Se3 trigonal pyramid and an Sb(V)Se4 tetrahedron sharing a common corner. The [Sb2Se5]4- anion in 4 is composed of two Sb(III)Se3 trigonal pyramids connected in the same manner as the [Sb2Se6]4- anion. The mixed-valent [Sb4Se9(4-)]n and [Sb2Se6]4- anions were not observed before. The synthesis and solid-state structural studies of the title compounds show that the transition-metal complexes exhibit different structure-directing effects on the formation of selenidoantimonates in dien. Extensive N-H...Se hydrogen bonds are observed between cations and anions in compounds 1-4, resulting in three-dimensional network structures. Optical and thermal properties of the compounds are reported.     

Solvothermal Syntheses of (H_2en)_2Sn_2S_6·en and[(H_2hmda)_3(Hhmda)_2](Sn_2S_6)_2Using SnCl_4 and S_8 as Starting Materials

1 INTRODUCTION Since Bedard et al. reported microporous tin(IV) sulfides synthesized by hydrothermal method in the presence of organic amine in 1989[1, 2], a number of thiostannates have been synthesized using hydro- or solvothermal techniques with organic amines as tem- plates. The structures of the resulting tin(IV) sulfi- des are related to the types of organic amines. Two- dimensional polyanions of the types of [Sn3S7]2- and [Sn4S9]2-, which are denoted as SnS-1 and SnS-3, respe…     

碱金属硒化物MHgSbSe~3(M=K,Rb, Cs)的晶体结构及其半导体性 质的研究

用有机溶剂热生长技术(SolvothermalTechnique)制备碱金属硒化物MHgSbSe~3(M=K,Rb,Cs),用单晶X射线衍射技术对其进行晶体结构分析,热分析结果表明,在常温(<200℃)下均为稳定的化合物。光学性质测试表明它们是半导体材料,KHgSbSe~3,RbHgSbSe~3,CsHgSbSe~3的禁带宽度依次为1.85eV,1.75eV,1.65eV。