溶剂热法CuInSe2粉体的形貌可控制备与表征

采用溶剂热法,通过改变反应温度和初始nCu/nIn比制备了一系列CuInSe2粉体。粉体的物相结构、形貌、光吸收性能分别用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)、紫外-可见分光光度计(UV-Vis)进行了表征。结果表明:180℃反应即可形成纯黄铜矿型CuInSe2粉体;随着反应温度的升高,粉体形貌有"片-片簇-球簇"的演变规律,其光吸收性能也随之增强,出现"红移"现象;初始nCu/nIn比能有效调控片簇的致密度。同时探讨了粉体不同形貌的形成机理。     

Synthesis and Crystal Structure of the Heteropolymate Compound Na3H2[Ce3(H2O)18Bi2W22O76]·23H2O

A Bi(Ⅲ) contained heteropolymate compound Na3H2[Ce3(H2O)18Bi2W22O76] (23H2O 1 has been synthesized. It crystallizes in the triclinic system, space group P with a = 14.370(3), b = 17.113(3), c = 24.764(5) A, α = 74.33(3), β = 77.20(3), γ = 65.29(3)o, V = 5285.3(18) A3, Z = 2, Mr = 6908.66, Dc = 4.341 g/cm3, F(000) = 6042, μ(MoKσ) = 28.543 mm-1, R = 0.0604 and wR = 0.1659 for 15788 reflections with I > 2σ(I). The structure analysis revealed that in the anionic framework of the title compound the [Bi2W22O76]14- anions are connected by Ce3+ and Na+ cations into a three dimensional network.     

Synthesis,Spectroscopic Properties and Crystal Structure of (C4N2H12)2Zr(C2O4)4·H2O

The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.     

镍螺旋化合物及其杂银配位聚合物的设计合成与结构

采用两个易扭转异构的双三齿有机配体，双吡啶二甲基-6,6′-二酰肼-2,2′-连吡啶(H₂L¹)和双吡啶二乙基-6,6′-二酰肼-2,2′-连吡啶(H₂L²)，和金属镍离子组装得到2个金属螺旋体(helicate)，Ni₂(HL¹)₂(PF₆)(BF₄)(CH₃OH)(H₂O)₂ (1)和Ni₂(HL²)(H₂L²)(ClO₄)₃(C₂H₅OH)(CH₃OH)H₂O)₃ (2),并测定了它们的晶体结构。同时由配体H₂L³出发,通过逐级组装的方法,得到一个镍-银杂金属的配位聚合物Ni₂Ag₂(HL³)₂(ClO₄)₂(CH₃CN)₃ (3)。单晶结构表明，配位聚合物3中配体H₂L³首先与镍离子组装成分子盒化合物(molecular box)，该结构单元进一步通过Ag离子与分子盒外围N原子配位，使分子盒互相串连成一维配位聚合物3，分子盒聚集体沿c方向伸展成一维链结构，链与链之间相互平行，进一步堆积成二维孔道结构。     

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver（I） Cluster

A new hexanuclear silver(I) compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound crystallizes in monoclinic,space group P2 1 /c with a=16.101(4),b=24.855(7),c=14.492(4),β=109.730(5)°,V=5459(3)3,C 90 H 102 Ag 6 N 24 O 6 S 6,M r=2455.54,D c=1.494 g/cm 3,μ(MoKα)=1.228 mm-1,F(000)=2472,Z=2,the final R=0.0761 and wR=0.1507 for 5258 observed reflections (I > 2σ(I)).In the structure,the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag 6 L 6 cluster.Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.     

配位吸附波测定微量铅的研究

本文研究了铅(Ⅱ)-4-(对-硝基苯偶氮)间苯二酚(AV)配合物在滴汞电极上的极谱行为。在pH 10.1的0.3 mol/L氯化钾介质中,铅(Ⅱ)-AV配合物于-0.61 V(vs.SCE)电位处产生一良好的吸附还原波,波高与铅的浓度在4.5×10~(-18)～1.3×10~(-6)mol/L范围内呈线性关系,检出限为2.5×10~(-8)mol/L。该方法用于头发、染料中微量铅的测定,结果满意。对极谱波的性质也进行了研究。     

若干多钒硼酸盐簇合物的光谱研究

合成了具有[(VO)₁₂O₆B₁₈O₄₂]簇骼的4种新颖的多钒硼酸盐簇合物：(enH₂)₆H₃[(VO)₁₂O₆B₁₈O₄₂]·13H₂O(1),[Ni(en)₂]₆H₃[(VO)₁₂O₆B₁₈O₄₂]·8H₂O(2),[Cu(en)₂]₅H₃[(VO)₁₂O₆B₁₈O₄₂][B(OH)₃]₂·16H₂O(3)和(enH₂)₄Na₄H₃[(VO)₁₂O₆B₁₈O₄₂]·8H₂O(4)。通过FTIR, UV-Vis DRS和荧光光谱等手段对其进行了研究,探讨了结构和性能的关系。其中,化合物(1)含有[(VO)₁₂O₆B₁₈O₄₂]的分立结构,环状B₁₈O₄₂通过8个B—(μ₃—O)—V键被两个V₆O₁₈簇夹在中间;而化合物(2)是在(1)的基础上,由6个[Ni(en)₂]各自通过两个Ni—(μ₃—O)—B与B₁₈O₄₂的桥氧配位形成另一类新的分立型结构;化合物(3)和(4)的[(VO)₁₂O₆B₁₈O₄₂]构筑单元间分别通过[Cu(en)₂]2+和无机Na+离子桥联形成二维层状结构。多钒硼酸盐簇合物的特征振动频率和这些化合物的结构相关;UV-Vis DRS表明,在205和260 nm附近出现金属氧簇化合物的荷移跃迁;用310 nm光激发, 在约415 nm处能引起由O_μ→Mo的荧光发射, 同时还研究了其荧光寿命。     

四核铜化合物(Cu4L4)(CH3CN)(H2L=(R)-1-(1-羟基正丁烷-2-氨甲基)萘-2-醇)的合成、晶体结构及磁性质

采用具有手性的席夫碱配体，(R)-1-(1-羟基正丁烷-2-氨甲基)萘-2-醇(H₂L)，和醋酸铜反应得到四核铜的化合物(Cu₄L₄)(CH₃CN)。用X-射线衍射对化合物的晶体结构进行了测定，结果表明此化合物含有4个铜和4个配体，铜通过配位作用和4个氧原子形成类立方烷中心。磁性测定表明此化合物中金属离子之间有弱的反铁磁相互耦合作用。