Synthesis,Crystal Structure,Spectroscopic Property and Redox Behavior of Zinc(Ⅱ) Complexes Containing Oligoaniline-functionalized Terpyridine Ligands

Two novel mono-nuclear zinc(Ⅱ) complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis (EA) and X-ray Diffraction (XRD). The UV-vis spectra show the ligand-centered (LC) π-π* transitions and intra-ligand charge transfer (1ILCT) transitions,and the 1ILCT band red-shifts with the increasing number of aromatic amine groups in the ligands. Complex [Zn(L1)2](PF6)2 with an aromatic amine group in ligand shows a strong emission peak at 523 nm in the MeCN solution at 293 K and a blue-shifted band at 517 nm in the alcoholic glass at 77 K. However,for complex [Zn(L2)2](PF6)2 containing aniline dimer modified ligand,no apparent emission can be observed in the MeCN solution at room temperature due to a PET non-radiative decay pathway. Both of them show multiplicate redox processes based on oligoaniline and terpyridine units. The shifts of redox potentials also reflect the D-A interactions between the oligoaniline units and [Zn(TPY)2]2+ core.     

Syntheses, Crystal Structures and Characterization of Two New Cadmium（II） Arsonates

Two cadmium arsonate coordination polymers, Cd(HL1)2 (1, H2L1 = 4-aminophenylarsonatic acid) and Cd(H2L2)2·2H2O (2, H3L2 = 2-(4-arsonphenylamino)acetic acid), have been synthesized and characterized by IR and single-crystal X-ray diffraction. Crystal data for 1: triclinic, space group P1 with a = 5.7559(12), b = 7.0903(14), c = 8.9925(18), α = 89.04(3), β = 80.79(3), γ = 85.09(3)o, Dc = 2.496 g·cm-3, μ = 6.095 mm-1, F(000) = 260, Z = 1, the final R = 0.0574 and wR = 0.1376 for 1489 observed reflections with I > 2σ(I). And those for 2: monoclinic, space group P21/c with a = 4.7595(10), b = 9.925(2), c = 22.609(5), β = 91.81(3)°, Dc = 2.167 g·cm-3, μ = 4.168 mm-1, F(000) = 684, Z = 2, the final R = 0.0335 and wR = 0.0815 for 2340 observed reflections with I > 2σ(I). The structure of 1 shows a two-dimensional layer consisting of inorganic chains of {CdN2(AsO3)2} along the a axis linking with the phenyl groups. These layers are further linked through strong interlayer hydrogen bonding interaction to form a three-dimensional hydrogen bond supramolecular architecture. Compound 2 has inorganic chains of {CdO2(AsO3)2} similar to 1, which connect with four adjacent inorganic chains forming a three-dimensional framework.     

Synthesis, Crystal Structure and Biological Activity of a Planar Copper Complex Derived from S-benzyldithiocarbazate

A planar transition metal complex Cu(L)2 (L = (E)-benzyl-2-(4-nitrobenzylidene)-hydrazinecarbodithioate) has been prepared and determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system,space group P21/c with a = 6.7101(11),b = 16.952(3),c = 13.962(3) ,β = 92.458(4)°,V = 1586.7(5) 3,Z = 4,Mr = 724.33,Dc = 1.516 g·m-3,μ = 0.998 mm-1,F(000) = 742,S = 1.021,R = 0.0634 and wR = 0.1077 for 813 observed reflections with Ⅰ 2σ(Ⅰ) and 205 parameters. In the molecular structure of the title complex,the copper atom exhibits a slightly distorted square-planar geometry in which the basal plane is defined by two N and two S atoms from two bidentate ligands. The complex was evaluated for its antitumor activity against two kinds of cell lines (MKN45 and HepG2) by MTT method. The preliminary bioassay indicates that the complex exhibits weak antitumor activity.     

Synthesis,Crystal Structure and Photoluminescence of a Three-dimensional Zinc(Ⅱ) Coordination Polymer with(20~3)_2(20)_3 Topology

The title compound,[Zn2(H2C4BIm)(ox)2]·2H2O(1,H2C4BIm = 2,2'-(1,4-bu-tanediyl)bis(1H-benzimidazole),has been synthesized by the hydrothermal reaction of Zn(NO3)2·6H2O with H2C4BIm and Na2C2O4 in water solution.It crystallizes in the triclinic system,space group P1 with a = 9.445(9),b = 9.598(9),c = 14.962(14) ,α = 72.160(10),β = 79.905(12),γ = 83.680(11)°,Mr = 633.18,V = 1269(2) 3,Z = 2,Dc = 1.657 g/cm3,F(000) = 644,μ = 1.953 mm-1,the final R = 0.0671 and wR = 0.1689.X-ray crystal structure analysis revealed that 1 is a 3D network with(203)2(20)3 topology in which the ZnII atom can be considered as a 3-connected node and both ox2-and H2C4BIm serve as the linear linkers.     

牛磺酸Schiff碱及其Cu（Ⅱ）配合物的合成与表征

用牛磺酸与2-吡啶甲醛反应合成了一种牛磺酸Schiff碱,并制备了它与Cu（Ⅱ）的配合物[CuL（H2O）].NO3,其中HL=C8H10N2O3S,利用元素分析,红外光谱,紫外光谱,差热-热重分析及摩尔电导的测定等方法对Schiff碱及金属配合物进行了表征。     

混合表面活性剂-铬天青S与铜显色反应研究及应用

在曲拉通X-100(TritonX-100)和乳化剂(OP)存在下,基于Cu2+-铬天青S(CAS)的显色反应,建立了分光光度法测定微量铜的新方法.通过Cu2+与CAS-Triton X-100-OP形成灵敏度较高的多元配合物,来测量铜含量.络合物的最大吸收波长为618nm,表观摩尔吸光系数为ε=6.62×105L·m...     

基于神光Ⅲ原型装置的成像型任意反射面速度干涉仪

 介绍了基于神光Ⅲ原型装置的成像型任意反射面速度干涉仪(VISAR)的系统结构和实验结果,详细阐述了为解决VISAR系统的光路对接调试、干涉仪零程差状态保持、探针激光方式、条纹相机触发时间等问题而采取的特殊手段。对系统性能进行了测试,结果表明:时间分辨力优于30 ps,空间分辨力优于10 μm,测速范围为10~50 km·s^-1。通过神光Ⅲ原型装置进行打靶实验,结果表明:该系统能获得透明材料中冲击波作用形成的清晰干涉条纹,能依据条纹分布情况来判断冲击波在空间不同位置的作用情况。对双灵敏度结构获得的两幅条纹图像进行处理,计算得到了冲击波在透明材料中的传播速度为36.5 km·s^-1。     

卟啉铜接枝SiO2有机-无机复合材料及强的非线性折射率

通过卟啉配合物Meso-四(4-羧基苯基)卟啉铜(简称Cu(Ⅱ)-TCPP)中的羧基与γ-氨基丙基三乙氧基硅烷(NH₂(CH₂)₃Si(OC₂H₅)₃,KH550)中的氨基的相互化学作用,成功地把卟啉配合物接枝到KH550中,随着KH550中乙氧基的水解与聚合反应的进行,卟啉铜连接到固体介质中,从而大幅度提高了卟啉在无机固体介质中的掺杂浓度. 将反应产物与γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(CH₂CHCH₂O(CH₂)₃Si(OCH₃)₃,KH560) 相杂化,形成物化性能良好、连接卟啉的有机-无机复合材料. 用红外光谱表征了Cu(Ⅱ)-TCPP与KH550的化学反应产物,用紫外—可见吸收光谱研究Cu(Ⅱ)-TCPP的分子状态. 应用Z扫描技术研究不同Cu(Ⅱ)-TCPP掺杂浓度的复合材料的非线性光学性质,其三介非线性折射率n₂达-1.1161×10^-16 m²/W. 关键词： 非线性折射率 有机-无机复合材料 接枝 Meso-四(4-羧基苯基)卟啉铜     

超强磁场下非掺杂ZnSe/BeTe Ⅱ型量子阱中激子和带电激子的光学特性

报道了液态氦温度(4.2 K)下非掺杂ZnSe/BeTe Ⅱ型量子结构中ZnSe势阱层内空间直接光致发光(PL)光谱的磁场依赖性(磁场高达53 T).实验结果显示,随着磁场的增加,激子和带电激子的PL强度呈现出相反的振动行为.当激子的PL强度增加时带电激子的PL强度减小,反之,当激子的强度减小时带电激子的强度却增加.并且在整个磁场范围内,这些振动呈现近似等间隔的周期性变化.这个行为被解释为费米能级与朗道能级的周期性共振,这个共振导致了处于费米能级上的二维电子气态密度的周期性调制. 关键词： 光致发光 二维电子气 带电激子 Ⅱ型量子阱     

高功率激光整形脉冲波形控制技术

 针对神光-Ⅲ原型装置物理实验要求的三台阶整形脉冲（三个台阶的脉冲宽度比为1.5∶1.0∶0.5,强度比为1∶4∶16,脉冲总能量为500 J）,并根据该装置的系统构成和具备任意脉冲整形技术,开展了高功率激光整形脉冲波形控制技术研究,通过对基频光段的增益饱和效应和三倍频光的频率转换过程的分析,获得了脉冲时间波形在传输、放大及频率转换过程中的一些变化特点,在此基础上建立了一套简单的预测模型。经过反复迭代计算和多次全系统联机实验获得了实验结果,并在物理实验中得到了应用,初步形成了高功率激光整形脉冲波形的控制方法。