二维网状Pd(Ⅱ)配合物的合成、晶体结构及电化学性质(英文)

A novel palladium(Ⅱ) complex [Pd(H2bpdc)Ala]Cl·3H2O (where H2bpdc is 2,2′-bipyridine-3,3′-dicar- boxylic acid and Ala is L-alanine) has been synthesized and characterized by IR spectra and elemental analysis. The crystal structure of the complex has been determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic system, space group P1 with a=0.685 5(2) nm, b=0.988 4(4) nm, c=1.349 6(4) nm, α=98.375(8)°, β= 97.900(15)°, γ=90.118(15)°, V=0.895 9(5) nm3, Z=2. In the molecule, Pd(Ⅱ) atom is four-coordinated and located at the centre of a planar quadrangle. The complex is assembled via intramolecular π-π stacking interactions and hydrogen bonds, which forms 2D network. The cyclic voltammetric behavior of the complex was also investigated.     

新型钯配合物[Pd(Phen)(TsserNO)]·H_2O的合成、晶体结构和体外抗肿瘤活性(英文)

A novel palladium(Ⅱ) complex [Pd(Phen)(TsserNO)]·H2O (Phen=1,10-phenanthroline; TsserNO=4- toluenesulfonyl-L-serinate dianion) has been prepared and structurally characterized, the cytotoxicity in vitro has also been investigated by MTT and SRB assays. The complex crystallizes in the monoclinic system, space group P21 with cell parameters a=0.618 64(14) nm, b=1.768 9(4) nm, c=0.990 2(2) nm, β=102.392(4)°, V=1.058 3(4) nm3 and Z=2. The complex had selectivity against HL-60, BGC-823, Bel-7402 and KB cells lines, its cytotoxicity is equal to that of cisplatin against BGC-823 and Bel-7402 cells lines, however it is less potent than cisplatin against HL-60 and KB cell lines.Keywordsantitumor; palladium(Ⅱ) complex; crystal structure     

溶液中选择识别Hg(Ⅱ)的基于罗丹明的荧光传感器

设计合成了一种可在含水体系中选择性识别Hg²⁺的荧光传感器(化合物1),该化合物中同时包含了作为信号输出基团的罗丹明6G和作为键合基团的2-取代吡啶。其结构得到了¹H NMR,ESI-HRMS和单晶X-ray衍射分析的确认。在混合的水体系中,该化合物对二价汞离子表现出高选择性和高灵敏度的荧光和显色传感,体系的发光伴随着汞离子的加入而得以增强,颜色由无色变成粉红色。荧光滴定、ESI-HRMS和Job曲线分析都显示该传感器分子和汞离子形成1∶1的配合物。     

偶氮胂Ⅲ—Ba(Ⅱ)共振散射光谱法测定人血清蛋白

在pH 3.0~3.8的BR缓冲溶液中,偶氮胂Ⅲ-Ba(Ⅱ)与蛋白质结合形成复合物,导致体系的共振散射信号增强,据此建立了蛋白质测定的共振散射光谱法。结果表明,在优化的实验条件下,牛血清白蛋白(BSA)的线性范围为0~1.0 mg/L,检出限为21.4μg/L;将该法用于人血清中蛋白质的测定,与医院测定结果基本一致;方法的批内精密度为2.8%(n=6),批间精密度为3.5%(n=6),回收率为96.0%~100.0%。     

1,10-邻菲咯啉-铜(Ⅱ)-L-丝氨酸/L-酪氨酸配合物的合成、SOD活性及电化学性质

合成了两个新的配合物:[Cu(Phen)(L-Ser)(H2O)]Cl(1)和[Cu(Phen)(L-Tyr)(H2O)]Cl.2H2O(2)(Phen=1,10-邻菲咯啉、L-Ser=L-丝氨酸、-LTyr=L-酪氨酸).用元素分析、摩尔电导率、红外光谱、紫外-可见光谱对配合物进行了表征.分别采用NBT光还原法和循环伏安法测定了配合物的SOD活性及电化学性质.结果表明,这些配合物具有较高的SOD活性,配合物1、2催化O2-.歧化分解速率常数KQ值分别为3.16×107和1.54×107mol-1.L.s-1.     

Nickel(II) N‐Benzyl‐N‐methyldithiocarbamato Complexes as Precursors for the Preparation of Graphite Oxidation Accelerators

The nickel(II) N‐benzyl‐N‐methyldithiocarbamato (BzMedtc) complexes [Ni(BzMedtc)(PPh₃)Cl] ( 1 ), [Ni(BzMedtc)(PPh₃)Br] ( 2 ), [Ni(BzMedtc)(PPh₃)I] ( 3 ), and [Ni(BzMedtc)(PPh₃)(NCS)] ( 4 ) were synthesized using the reaction of [Ni(BzMedtc)₂] and [NiX₂(PPh₃)₂] (X = Cl, Br, I and NCS). Subsequently, complex 1 was used for the preparation of [Ni(BzMedtc)(PPh₃)₂]ClO₄ ( 5 ), [Ni(BzMedtc)(PPh₃)₂]BPh₄ ( 6 ), and [Ni(BzMedtc)(PPh₃)₂]PF₆ ( 7 ). The obtained complexes 1 – 7 were characterized by elemental analysis, thermal analysis and spectroscopic methods (IR, UV/Vis, ³¹P{¹H} NMR). The results of the magnetochemical and molar conductivity measurements proved the complexes as diamagnetic non‐electrolytes ( 1 – 4 ) or 1:1 electrolytes ( 5 – 7 ). The molecular structures of 4 and 5· H₂O were determined by a single‐crystal X‐ray analysis. In all cases, the Ni^II atom is tetracoordinated in a distorted square‐planar arrangement with the S₂PX, and S₂P₂ donor set, respectively. The catalytic influence of selected complexes 1 , 3 , 5 , and 6 on graphite oxidation was studied. The results clearly indicated that the presence of the products of thermal degradation processes of the mentioned complexes has impact on the course of graphite oxidation. A decrease in the oxidation start temperatures by about 60–100 °C was observed in the cases of all the tested complexes in comparison with pure graphite.     

草酸根桥联手性双核铜的合成、表征、结构与磁性

分别以(8R,10R)-(-)-[4,5]-pineno-2,2′-bipyridine或(8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine(LRR和LSS)为手性配体合成双核铜络合物[Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2](1)、[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a)、[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2](2)和[Cu2(μ-ox)-(LRR)(LSS)(CH3COCH3)2(ClO4)2](3)(ox2-=草酸根),并探讨了其反应机理.由元素分析、电导率、紫外可见谱(UV-vis)、圆二色(CD)谱和晶体结构分析推测:该系列络合物具有草酸根桥联的双核结构,两个铜(II)离子与草酸根几乎成共平面;1a和3的晶体结构分析表明,每个Cu(II)的配位构型为拉长畸变八面体,双核分子中轴向的两个溶剂分子和两个高氯酸根互为反式配位.对映体络合物1和2的溶液CD光谱大致呈镜像对称,在可见区的极弱CD吸收峰可能源于LRR和LSS蒎烯基上的手性中心对Cu(II)d-d生色团的手性微扰产生的邻位效应.采用最小二乘法和Bleaney-Bowers方程对络合物1的变温磁化率测试数据进行拟合,求得交换积分J=-338.41(4)cm-1,表明铜(II)离子间有较强的反铁磁自旋交换作用.     

[(NHC)CrCl(μ-Cl)(THF)]_2 and(NHC)_2CrCl_2(NHC=1,3-Diisopropyl-4,5-dimethylimidazole-2-ylidene):Syntheses,Structures,and Polymerization Activities

The preparation of divalent chromium N-heterocyclic carbene(NHC,1,3-diisopropyl4,5-dimethylimidazole-2-ylidene) compounds is reported.The reaction of 1:1 molar ratio of NHC with CrCl2 led to an isolation of [(NHC)CrCl(μ-Cl)(THF)]2(1),while that of 2:1 ratio resulted in the formation of(NHC)2CrCl2(2).1 can be considered as an intermediate in the formation of 2 and further converted into 2 by the addition of another equiv.of NHC.The reaction of 2 with CpNa afforded an ion pair compound [(NHC)2CrCp]+[Cp]-(3),indicating a strong coordination ability of NHC supplanting one of the ionic Cr-Cp bonding.In combination of methylalumoxane(MAO) as cocatalyst 1 and 2 both are active for catalyzing ethylene polymerization.     

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.