Thermochemistry of Ternary Complex Dy(Et_2dtc)_3(phen)

The ternary solid complex was synthesized with sodium diethyldithiocarbamate (NaEt_2dtc), 1,10-phenanthroline (phen) and low hydrated dysprosium chloride in absolute ethanol by improved method of reference. The title complex was identified as the general formula of Dy(Et_2dtc)_3(phen) by chemical and elemental analyses. IR spectrum of the complex shows that the Dy^(3+) coordinated with six sulfur atoms of three NaEt_2dtc and two nitrogen atoms of phen. It is assumed that the coordination number of Dy^(3+) is eight.The enthalpy change of liquid-phase reaction of formation, Δ_rH~θ_m(l), is determined as (-19.091±0.015) kJ·mol^(-1) at 298.15 K by a microcalorimeter, and the enthalpy change of the solid-phase reaction of formation, Δ_rH~θ_m(s), is calculated as (139.641±0.482) kJ·mol^(-1) on the basis of a thermochemical cycle. The thermodynamic of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex, Δ_cU, is determined as (-16730.21±9.25) kJ·mol^(-1) by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpies of combustion, Δ_cH~θ_m, and standard enthalpies of formation, Δ_fH~θ_m, are calculated as (-16749.42±9.25) kJ·mol^(-1) and (-2019.68±10.19) kJ·mol^(-1), respectively.

Synthesis and Properties of Ru(phen)_2(phen-NHCOCH_2Br)(PF_6)_2

A new active material for ECL sensor. Ru(phen)2(phen-NICH2Br)(PF6)2 has beendesigned and synthesized. its structure was confirmed by means of IR. MS and 'H NMR. Also.some of its properties such as electrochemstry. fluorescence and ECL are reported.

Synthesis, Characterization and Thermal Decomposition of Ln(Me_2dtc)_3(phen)

Four solid complexes of Ln(Me2dtc)3(phen) (Ln=Eu, Gd, Tb, Dy) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligands of sodium dimethyldithiocarbamate and 1, 10-phenanthroline·H2O (abbreviated as phen·H2O), and characterized by elemental analysis, IR spectroscopy, TG-DTG and X-ray diffraction techniques. Combining with the crystal structures, the complexes are identified as the general formula of Ln(Me2dtc)3(phen). TG-DTG with X-ray powder diffraction showed that these compounds could decompose to lanthanide sulfides under relatively lower temperature, which indicated that the title complexes could be ideal precursors to prepare lanthanide sulfides.

晶态配合物荧光材料[Ni(3,5-(SO_3)_2CatH_2)(phen)_2(H_2O)]·4H_2O的合成、结构及性质

利用缓慢蒸发溶剂法合成了单核镍(Ⅱ)配合物[Ni(3,5-(SO3)2CatH2)(phen)2(H2O)]·4H2O(CatH2=1,2-二羟基苯,phen=1,10-邻菲罗啉)。利用X-射线单晶衍射、元素分析、红外光谱、热重分析和荧光光谱等对其进行了表征。结果表明,该配合物属于三斜晶系,P1空间群。镍离子与一个1,2-二羟基苯-3,5-二磺酸根离子、两个1,10-邻菲罗啉配体和一个水分子配位,形成[Ni(3,5-(SO3)2CatH2)(phen)2(H2O)]结构。在结构单元中,还有四个未配位的水分子。未配位的水分子和[Ni(3,5-(SO3)2CatH2)(phen)2(H2O)]结构通过O-H…O氢键相连,形成三维网状结构。与配体相比,配合物的荧光发射谱发生红移,发射峰在645 nm。荧光寿命为1.07 ns。

DNA分子光开关钌配合物[Ru(phen)_2(dppz)]^(2+)的研究进展

综述了近20年来典型的DNA-分子光开关钌(Ⅱ)多吡啶类配合物[Ru(phen)2(dppz)]2+在实验和理论上的研究进展与应用。阐明了该配合物的结构特征及其与DNA的作用机理、作用模式以及在一些相关热点问题上的争议,同时还介绍了该配合物在DNA-结构识别及定量分析等方面的重要应用。基于此,还对DNA-分子光开关钌配合物的开发作了展望。

Friedel-Crafts Acylation Reactions Using Catalytic SbCl_5-TEBA Complex as an Efficient Catalyst

SbCl_5-TEBA (PhCH_2NEt_3Cl) complex catalyzes the Friedel-Crafts acylation reactionsefficiently.

A Novel Degradation Pathway of Zn(dmid)(phen)_2 in Pyridine

The light-oxidation degradation processes of Zn(dmid)(phen)_2 ( dmid = 4,5-dimercapto-l, 3-dithiole-2-one, phen = 1,10-phenanthroaline) in pyridine solvent has beenmonitored. It has been found under the light, dmid^(2-) of Zn(dmid)-(phen)_2 in pyridine solutioncould generate NCS~ and NCS^-replaces dmid^(2-) to form Zn(NCS)_2 (phen)_2 simultaneously. Thecrystal structure of Zn(NCS)_2 (phen)_2 has been determined. In the crystal of Zn(NCS)_2 (phen)_2,two NCS~ ligands are arranged in syn-configuration, and there is strong pi-pi interaction betweenthe two adjacent parallel phen.

A Porous 3D Supramolecular Architecture of Cd(II) Complex with Water Clusters as Pillars

A supramolecular complex of Cd（II） with 1D water tapes as pillars[Cd2（dpa）2（phen）2（H2O）2]·6H2O 1 （H2dpa = diphenic acid, phen = phenanthroline）, has been synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1^- with a = 9.7029（4）, b = 11.9601（5）, c = 12.1788（4） A, α = 71.6990（10）, β = 71.8740（10）, γ = 74.4680（10）°, V = 1252.39（8） A^3, C52H48Cd2N4O16, Mr = 1209.76, Z= 1, Dc = 1.604 g/cm^3,μ = 0.925 mm^-1, F（000） = 612, R = 0.0679 and wR = 0.2514 for 3870 observed reflections （I 〉 2σ（I））. Two intramolecular Cd（II） centers of this complex are encircled by two dpa^2- ligands forming an 18-membered ring, which is further assembled into a pillared three-dimensional （3D） supramolecular architecture through the synergetic effect of intermolecular face-to-face π…π stacking and weak O-H…O hydrogen-bonding interactions. Moreover, this complex exhibits photoluminescence with the main emission bands located at about 456 nm upon excitation at 355 nm in the solid state at room temperature.

[Ru（bpy）2（phen）]^2＋主配体上双取代效应DFT法研究

对钌联吡啶菲咯啉配合物[Ru(bpy)2(phen)]2+及其主配体(phen)上5,6-双取代衍生物,用密度泛函(DFT)法在B3LYP/LanL2DZ水平上进行理论计算研究.探讨供电子基团(OH)和拉电子基团(F)在主配体上的取代对配合物的电子结构及相关性质,如配合物前沿分子轨道的能量、组成、光谱性质、原子的净电荷布居及配位键长键角等的影响规律.计算结果表明,取代基对该系列取代衍生物的电子结构,特别是第一激发态的电子云分布影响较大,拉电子基团(F)能活化主配体,钝化辅助配体;而供电子基团(OH)则相反.无论是供电子基团(OH),还是拉电子基团(F)都导致取代衍生物的电子基谱带红移.此外,用基于极性交替规律及极性叠加概念的多系列箭头的图示方法对主配体上的原子净电荷布居的特征作了讨论.计算结果能较好地解释有关的实验现象与规律.

Synthesis, Electrochemistry, Fluorescence and ECL of Ru （phen）2 （dcbpy） （PF6）2

A new ECL-active species. Ru (phen)_2 (dcbpy) (PF_6)_2. has been designed andsynthesized. its structure was confirmed by means of IR. ESI-MS and 2D NMR. Also. itsproperties of electrochemistry. fluorescence and ECL are reported. which have suggested a goodhope of being used in electrochemiluminescent immunoassay and nucleic acid hybridization.

Determination of combustion energies and the standard enthalpies of formation for the complexes of RE(Et_(2)dtc)_(3)(phen)

Solid complexes,RE(Et_(2)dtc)_(3)(phen)(RE=La,Pr,Nd,Sm-Lu),were synthesized with sodium diethyldithiocarbamate(NaEt_(2)dtc3H_(2)O),1,10-phenanthroline(o-phen·H_(2)O)and hydrated lanthanide chlorides in absolute ethanol.The constant-volume combustion energies of complexes,Δ_(c)U,were determined by a precise rotating-bomb calorimeter at 298.15 K.The standard enthalpies of combustion,Δ_(c)H^(θ)_(m),and standard enthalpies of formation,Δ_(f)H^(θ)_(m),were calculated for these complexes,respectively.The experiment results showed the'tripartite effect'of rare earth.

溶胶-凝胶-钴-邻菲啰啉修饰电极对一氧化氮的电催化氧化及其测定

报道了溶胶 凝胶 钴 邻菲口罗啉膜修饰电极的制备方法及其在一氧化氮(NO)检测中的应用,采用循环伏安法(CV)研究修饰电极的电化学特性,差示脉冲伏安法(DPV)对NO进行检测。该修饰电极对NO的电化学氧化具有很好的催化作用,使其氧化电位负移了210mV,氧化峰电流与NO浓度在5.6×10-8～2.8×10-5mol/L范围内呈良好的线性关系,相关系数r=0.999,检测限为1.4×10-8mol/L,且生物体内常见的干扰物质如抗坏血酸、NO2-和儿茶酚胺类神经递质的代谢物等不干扰测定。

铜(Ⅱ)配合物与DNA作用的光谱法研究

采用紫外光谱和荧光光谱研究了配离子 [Cu(A) 2 ]2 +(其中A =邻菲络啉 ( phen) ,联吡啶 (bpy) ,乙二胺 (en) )与小牛胸腺DNA的相互作用。实验发现配合物的存在使DNA碱变性的 pH增大 ,变性后增色效应减小。EB DNA体系的荧光强度随 [Cu( phen) 2 ]2 +的加入迅速减弱。在DNA存在下 ,配离子被猝灭剂 [Fe(CN) 6]4-的发光猝灭程度减小。进一步研究了配体分子平面的大小对配合物与DNA作用的影响。结果表明 ,铜配合物与DNA之间发生了插入作用 ,且该作用随配体芳环平面的减小而减弱 ,即 [Cu( phen) 2 ]2 +>[Cu(bpy) 2 ]2 +>[Cu(en) 2 ]2 +。

Coordination chemistry of organometallic polydentate ligand Reactive chemistry of the tridentate ligand trans-Fe(Ph_2PQu-P)_2- (CO)_3 [Ph_2PQu=2-diphenyl-phosphino-4-methylquinoline] and molecular structure of [Fe(CO)_3(μ-Ph_2PQu)_2HgI]^+[HgI_3]

Reaction of a new type of bidentate ligand PhPQu [ PhPQu = 2-diphenylphosphino-4-methylquinoline] with Fe(CO)5 in bu-tanol gave trans-Fe(PhPQu-P)(CO)3 (1).Compound 1,which can act as a neutral tridentate organometallic ligand,was reacted with I B,II B metal compounds and a rhodium complex to give six binuclear complexes with Fe-M bonds,Fe(CO)3(u-Ph2PQu)MXn(2-7) [M=Zn(Ⅰ),Cd(Ⅱ),Hg(Ⅱ),Cu(Ⅰ),Ag(Ⅰ),Rh(Ⅰ)],and an ion-pair complex [Fe(CO)3(n-Ph2PQu)2HgI][HgI3]- (8).The structure of 8 was determined by X-ray crystallography.Complex 8 crystallizes in the space group P-1 with a=1.0758(3),b= 1.6210(4),c = 1.7155(4) nm; a = 75.60(2)β=71.81(2),Y = 81.78(2) and Z = 2 and its structure was refined to give agreement factors of R =0.050 and Rw = 0.057.The Fe-Hg bond distance is 0.2536 nm.

苯甲酸与含氮配体构筑的两种铅配合物的水热合成、结构与性质研究(英文)

用水热合成方法得到了2个二价铅配合物[Pb(BA)2(phen)].(HBA)(1)及[Pb(2,2′-bipy)(BA)(NO3)]n(2)(HBA=benzoic acid;phen=1,10-phenanthroline;2,2′-bipy=2,2′-bipyridine),对它们进行了元素分析、红外光谱、荧光光谱、粉晶衍射及热分析表征,并通过X-射线单晶衍射测定了配合物的单晶结构。X-射线单晶结构解析表明,配合物1与2均属三斜晶系,P1空间群。化合物1中,弱Pb…O相互作用、分子间氢键及π…π堆积作用共同构筑了配合物1的三维框架结构。铅的6s孤电子具有立体化学活性,使配位键分布于半球型区域。化合物2中,相邻的PbⅡ离子通过螯合-桥联的硝酸根联结成一维链状结构,广泛存在的π…π堆积作用将邻近的一维链堆积成三维超分子结构。化合物2中的6s孤对电子未显示出立体化学活性,其配位键近似分布于全球型区域。

2-巯基苯并噻唑Zn(Ⅱ)和Cd(Ⅱ)配合物的一步法合成及其谱学性质

Zn(NO3)2.6H2O和Cd(NO3)2.4H2O与2-巯基苯并噻唑(2-Hmbt)及L配体(L=2,2′-bipy,1,10-phen)反应,用绿色化学的合成方法得到了三种三元配合物Zn(C7H4NS2)2(2,2′-bipy)(1)、Zn(C7H4NH2)2(1,10-phen)(2)和Cd(C7H4NS2)2(2,2′-bipy)(3),三种配合物均采用红外光谱、元素分析对配合物的组成、结构和光谱性质进行了测试和表征,(1)用1H核磁共振谱进行了性质测试与表征.

天冬氨酸-邻二氮菲-Cu(II)配合物与DNA相互作用及其对DNA的降解

利用循环伏安法研究天冬氨酸-邻二氮菲-Cu(II)配合物([Cu(Phen)(Asp)]2+)与脱氧核糖核酸(DNA)之间的相互作用.结果表明,在pH 6.8的磷酸盐缓冲溶液中,配合物[Cu(Phen)(Asp)]2+产生一对灵敏的氧化还原峰,峰电流随DNA浓度的增大而逐渐降低.在最佳实验条件下,测定线性范围为0.02-10.05μg/mL,检出限为0.002μg/mL,且研究该配合物存在条件下对DNA的电化学诱导降解.

金属铁与氟尿嘧啶配合物的体内抗肿瘤活性及其毒性

背景:前期研究表明,金属铁与氟尿嘧啶、邻菲罗啉的配合物具有良好的体外抗肿瘤活性,能抑制多株人癌细胞的增殖。目的:检测新型金属铁与氟尿嘧啶、邻菲罗啉配合物[Fe(5-Fu)_2(Phen)SO_4]的体内抗肿瘤活性及毒性。方法:将40只昆明小鼠随机分为4组,分别腹腔注射72,102.9,147,210 mg/kg的[Fe(5-Fu)_2(Phen)SO_4]配合物,检测配合物的半数致死量。建立昆明小鼠S180移植性肉瘤模型,造模后第2天随机分8组,分别腹腔注射[Fe(5-Fu)_2(Phen)SO_4]配合物15 mg/kg(低剂量组)、[Fe(5-Fu)_2(Phen)SO_4]配合物30 mg/kg(中剂量组)、[Fe(5-Fu)_2(Phen)SO_4]配合物60 mg/kg(高剂量组)、生理盐水(阴性对照组)、顺铂(阳性对照组)、5-氟尿嘧啶、铁盐与邻菲罗啉,1次/d,连续注射7 d后,检测肉瘤质量、小鼠体质量及主要脏器系数,以及主要脏器病理组织学变化。结果与结论:[Fe(5-Fu)_2(Phen)SO_4]配合物的半数致死量为103.9 mg/kg。与阴性对照组比较,高剂量组、阳性对照组、5-氟尿嘧啶组可明显抑制肿瘤的生长(P<0.05或P<0.01),且以高剂量组效果最明显(P<0.01)。60 mg/kg[Fe(5-Fu)_2(Phen)SO_4]配合物对肾脏的抑制作用较顺铂弱,但对小鼠肝脏、脾脏、胸腺的抑制作用较顺铂强,提示配合物的肾毒性较顺铂低,但有较强的免疫毒性及肝毒性。

靶向端粒G-四链体手性钌配合物的抗肿瘤活性研究

[目的]研究手性钌配合物Λ-[Ru(bpy)2(pyip)]2+(Λ-OMe)、Δ-[Ru(bpy)2(pyip)]2+(Δ-OMe)及其外消旋化合物[Ru(phen)2p-MOPIP]2+(dl-OMe)在体外实验中的抗肿瘤活性。[方法]3种配合物分别作用于人胃癌细胞株(MGC-803),人结肠癌细胞株(Colo205),人乳腺癌细胞株(MCF-7),人肺腺癌上皮细胞株(A549),人肝癌细胞株(Hep G2),人舌鳞状细胞癌株(SCC-9)48 h,以人胃黏膜上皮细胞株(GES-1)为正常对照细胞株,顺铂为阳性对照药物,四甲基偶氮唑蓝(MTT)法筛选出其中半抑制浓度(IC50)最小的药物和药敏作用最好的肿瘤细胞。筛选出药物和肿瘤细胞后,再用MTT法测定24、48、72 h相应药物对肿瘤细胞的抑制作用;Hoechest33342染色法测定其对肿瘤细胞的凋亡诱导作用。[结果]MTT法筛选出Λ-OMe对胃癌MGC-803细胞的增殖抑制作用最好,即(IC50)最小,在作用48 h的半数抑制浓度为:7.4 mg/L,且呈现很好的时间和剂量依赖性。Hoechest33342染色显示,在药物处理48 h后,随着药物浓度增加,药物促凋亡作用越明显。[结论]手性钌配合物具有良好的抗肿瘤活性,其中以Λ-OMe抗肿瘤活性最好。

ELECTROREDUCTION MECHANISM OF Ni(DMG)-2 COMPLEX STUDIED WITH QUANTUM CHEMICAL METHOD

The electronic structures of the species Ni(DMG)_2, (Ni(DMG)_2)^- and (Ni(DMG)_2)_(2-) have been studied by INDO quantum chemical method. The results have clearly shown that in the first stage of the electroreduction of Ni(DMG)_2, one electron interacts with the d orbitals on the nickel atom, while in the further stage the second electron interacts with the p orbitals on the nitrogen atoms. It conforms with our electrochemical experimental studies which showed that not only Ni(Ⅱ) is reduced but also DMG is catalytically reduced during the reduction of Ni(DMG)_2.