以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

Two new binuclear Fe(Ⅲ)-Fe(Ⅲ) and Mn(Ⅱ)-Mn(Ⅱ) complexes containing the dianions of chloranilic acids (CA) which act as bridging ligand in the complexes, have been synthesized namely [Fe₂(phen)₄(u-CA)](ClO₄)₄·2H₂O and [Mn₂(phen)₄(u-CA)](ClO₄)₂·3H₂O (phen = O-phenanthroline; CA = dianions of chloranilic acids). They have been characterized by elemental analyses, IR, electronic spectra, susceptibility and variable-temperature magnetic susceptibility. The results indicate that there is a antiferromagnetic interaction between metal ions in the complexes at low temperature. The observed data were well fitted to those from a Heisenberg model. The obtained parameters: J= -2.02cm^-1, g = 2.25 for Fe(Ⅲ)-Fe(Ⅲ) complex; J=-5.45cm^-1, g = 2.01 for Mn(Ⅱ)-Mn(Ⅱ) complex.     

三种1,10-邻菲咯啉-铜(Ⅱ)-L-氨基酸配合物与DNA的相互作用

The Interaction of three complexes [Cu(phen)(Gly)(H₂O)]·ClO₄·2.5H₂O (1), [Cu(phen)(L-Val)(H₂O)]·ClO₄ (2) and [Cu(phen)(L-Ile)(H₂O)]·ClO₄ (3) (phen=1,10-phenanthroline, Gly=glycinate, L-Val=L-valinate, L-Ile=L-isoleucinate) with DNA have been investigated by electronic absorption spectroscopy, ethidium bromide(EB) fluorescence spectroscopy, viscosity and gel electrophoresis measurements. The intensity of maximal absorption peaks from absorption spectra are weakened with dropping DNA into the complexes. The emission intensity of EB-DNA systems in fluorescence spectroscopy have descended 50%, when the data of C_Cu / C_DNA is 30～40. Moreover, the viscosity of DNA increase and then decrease with the increasing of complexes. All of the results indicate that the interaction of complexes with DNA are partial intercalation, and the result of agarose gel electrophoresis show that the complexes can cleave pBR322 DNA in the present of H₂O₂ / vitamin C.     

N，N′-双(2-吡啶甲基)二硫代草酰胺根桥联的三核铜(Ⅱ)配合物的合成及表征

Two new trinuclear copper(Ⅱ) complexes bridged with N,N′-Bis(2-pyridylmethyl)-Dithiooxamidate, ［Cu₃L₂］(ClO₄)₂(1) and ［Cu₃L₂］(NO₃)₂(2) (H₂L=N,N′-Bis(2-pyridylmethyl)-Dithiooxamide), have been synthesized, and characterized by elemental analyses, IR, UV-visible spectra, conductance and EPR spectra. The variable temperature magnetic susceptibility for complex (1) has been measured in the range of 1.5～298K. Experimental data of magnetic susceptibility are successfully fit to theoretical value based on the spin Hamiltonian operator: H=-2J(S₁S₂+S₂S₃)-2J′S₁S₃, S₁=S₂=S₃=1/2, giving the magnetic exchange parameters of 2J=-170 cm^-1 and 2J′=-7.2 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Cu(Ⅱ) ions.     

New Ni(Ⅱ)Cu(Ⅱ)Ni(Ⅱ) trinuclear complexes with an S=3/2 high-spin ground state

Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-1,10-phenanthroline(NO2-phen) (2), 2,2'-bipyridyl(bpy) (3) and 4,4'-dimethyl-2,2'-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)2.3H2O has been studied in the 4-300 K range, giving the exchange integral J=-109 cm-1. The MT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.     

N，N′-双(2-吡啶乙基)二硫代草酰胺根桥联的三核铜(Ⅱ)配合物的合成及性质

Two Trinuclear copper(Ⅱ) complexes bridged with N,N′-Bis(2-pyridylethyl)-Dithiooxamidate, [Cu₃L₂](ClO₄)₂ (1) and [Cu₃L₂](NO₃)₂ (2) (H₂L=N,N′-Bis(2-pyridylethyl)-Dithiooxamide), have been synthesized, and characterized by elemental analyses, IR, UV-Visible spectra, conductance and EPR spectra. The variable temperature magnetic susceptibility for complex 1 has been measured in the temperature range of 1.5～298 K. Experimental data of magnetic susceptibility are successfully fit to theoretical value based on the spin Hamiltonian operator：(?), S₁=S₂=S₃=1/2, giving the magnetic exchange parameters of 2J=-221.6 cm^-1 and 2j=-15.8 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Cu(Ⅱ) ions.     

二硫代草酸根桥联的双核镍(Ⅱ)配合物研究

Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni₂(Bpy)₃(Dto)₂(H₂O)₃(1), Ni₂(Phen)₃(Dto)₂(H₂O)₃(2) and Ni₂(Me₂Bpy)₃(Dto)₂(H₂O)₂ (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline, Me₂Bpy=4,4′-dimethyl-2,2′-bipyridine, Dto^2-=Dithiooxalate), and characterized by elemental analyses, IR, UV-Visible spectra, conductance. The variable temperature magnetic susceptibilities for the complexes were measured in the range of temperature between 1.5 K and 298 K. Experimental data of magnetic susceptibility were successfully fit to theoretical value based on the spin Hamiltonian operator：(?), S₁=S₂=1, giving the magnetic exchange parameters of 2J=-52.8 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions. The magnetic exchange parameters of the binuclear Nickel(Ⅱ) complexes bridged with dithiooxalate is larger than that of the binuclear Nickel(Ⅱ) complexes bridged with oxalate. Dithiooxalate is more effective to transfer antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions than oxalate.     

含有双螺旋链的配位聚合物[Co(dpa)prz0.5]n的合成、晶体结构及磁性质

A coordination polymer [Co(dpa)prz_0.5]_n(1) with double-helix chains has been constructed hydrothermally using H₂dpa (H₂dpa=diphenic acid), prz (prz=piperazine) and Co(NO₃)₂·6H₂O. The structure and magnetic properties of the complex were investigated. The complex crystallizes in triclinic system and P1 space group. Each Co atom is five-coordinated and takes a distorted tetragonal pyramid geometry. Two carboxylates of the H₂dpa ligands bridge four Co(Ⅱ) ions to form infinite right-handed or left-handed helical -C-O-Co- chains. The two types of helical chains are interconnected to each other through the Co(Ⅱ) centers to produce double-helix chains. The chains form a 2D sheet through the coordination interaction of prz molecules between adjacent chains. The sheets are further interlinked by hydrogen bond interactions to generate 3D coordination frameworks. Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Co(Ⅱ) ions. CCDC: 709275.     

双核铜(Ⅱ)配合物在H2O2存在下对DNA的氧化切割活性

A novel dinuclear copper(Ⅱ) complex, [Cu₂(phen)(dipic)₂(H₂O)₂]·2H₂O (phen=1,10-phenanthroline, dipicH₂=2,6-pyridinedicarboxylic acid), has been prepared and structurally characterized. The complex crystallizes in the triclinic system, space group P1 with cell parameters a=0.846 0(17) nm, b=1.289 5(3) nm, c=1.452 7(3) nm, α=77.42(3)°, β=79.11(3)°, γ=87.08(3)°, and V=1.518 8(6) nm³. The dinuclear complex shows potential DNA cleavage activity at micromolar concentration in the presence of H₂O₂ and exhibits higher nuclease efficiency than mononuclear complex [Cu(dipic)(H₂dipic)]·H₂O. Without external reductants, the added H₂O₂ may contribute to the generation of hydroxyl radicals that result in DNA strand scission.CCDC:291786.     

配合物[1-(4′-fluorobenzyl)pyridinium]2[Ni(dto)2](dto2-=dithiooxalate dianion)的合成及晶体结构

The complex [1-(4′-fluorobenzyl)pyridinium]₂[Ni(dto)₂] (dto^2- means dithiooxalate dianion) has been pre-pared by reaction of Na₂[Ni(S₂C₂O₂)₂] and the 1-(4′-fluorobenzyl)pyridinium chloride salt. The crystallographic data for the title complex: triclinic P1, a=8.5698(8)?, b=9.3461(9)?, c=10.5361(10)?, α=67.177(2)°, β=67.398(2)°, γ=79.611(2)°, V=717.59(12)?³, Z=1. The [Ni(dto)₂]^2- anion with the Ni atom lying on an inversion center and exhibits a quasi-planar structure. An extensive hydrogen bond network of C-H…O is clearly observed. The nature and size of cation seems to play an important factor in the type of intermolecular interactions as well as the crystal packing in this kind of complexes.     

Yb(Cl4)3·3H2O-18C6-C2H5OH体系(25℃)的相化学研究及固态配合物的合成与性质

The solubilities of Yb(ClO₄)₃·3H₂O-18C6-C₂H₅OH ternary system at 25 were invstigated by a semimicro method for study of phase equilibrium.and the refractive indexes of saturated solutions were determined.The behavior of water in this system during the equilibrium was examined.The results indicate that there are two kinds of complexes formed in the system, their chemical compositions are: Yb(ClO₄)₃·18C6·3H₂O·2C₂H₅OH (I) and Yb(ClO₄)₃ 18C6·3H₂O·C₂H₅OH.Both are incongruently soluble in EtOH.The influences of rare earth ions and salt anions on formation of complexes were discussed.The two solid complexes have been prepared, and their composihons and properties have been investigated by chemical analysis, IR, DTG and DSC.According to the DSC, the enthalpies of some steps during the decomposition have been obtained for complexes (Ⅲ)and (Ⅳ).     

双(4，5-二氮杂芴酮)缩对，对′-二氨基二苯甲烷桥联的二(邻菲咯啉合铜(Ⅱ))的合成及其与DNA作用的光谱研究

A new bimetallic Cu(Ⅱ) complex， [(phen)Cu(μ-bdmp)Cu(phen)](ClO₄)₄·2H₂O， where phen and bdmp denote 1，10-phenanthroline and 1，1′-bis(nitrilomethylidyne-4，5-diazafluoren)-4，4′-(μ-methylene)bisphenyl re-spectively was synthesized and its DNA binding behavior was studied by photophysical methods. It has been found that calf thymus DNA could result in significant decrease both in electronic absorption and fluorescent emission of the complex. The fluorescence quenching by ferrocyanide could be reduced to some extent for the complex in presence of DNA. These facts suggest that this dicopper(Ⅱ) complex binds to double helix DNA by partial inter-calation.     

新型铂(Ⅱ)类配合物的合成、表征和抗肿瘤活性

Seven novel platinum(Ⅱ) complexes[Pt(Ⅱ)(NH₃)(H₂O)X](Ⅰ～Ⅶ) {X=(COO^-)₂(oxalato), 2p-CH₃O-C₆H₄-COO^-(p-methyoxbenzolato), 2C₆H₅-COO^-(benzolato), 2CH₃COO^-(acetato), (CH₂)(COO^-)₂(malonato), (CH₂)₂(COO^-)₂(succinato), (CH=CH)(COO^-)₂(maleato)} have been prepared and characterized by elemental analysis, thermal analysis，IR, UV, and ¹H NMR spectroscopy. The antitumor activities of these complexes in vitro against EJ、HCT-8, KB, BGC-823, Bel-7402, HL-60, MCF-7 and Hela cell lines have been studied. Complex Ⅰ and Ⅴ show remarkable antitumor activities against EJ cell line, and the inhibitory rate is 45.96% and 54.32% at concentration of 10 μmol·L^-1, respectively. The inhibitory rate of the complexes Ⅱ and Ⅲ is greater than 50% against HL-60, BGC-823, KB and EJ cell lines. The inhibitory rate of the complex Ⅵ is 51.89% and 57.96% against BGC-823 and EJ cell lines. The complexes Ⅳ and Ⅶ have no antitumor activities against tested tumor cell lines. The complexes Ⅱ, Ⅲ and Ⅵ can stem the cell cycle of HL-60 on the G₂+M.     

钐与1-苯基-2，3-二甲基-4-酰代吡唑酮-5的三元配合物的合成与表征

Four new Sm(Ⅲ) ternary complexes with 1-phenyl-2,3-dimethyl-4-acethlpyrazolone-5 (HPDMAP) or 1-phenyl-2,3-dimethyl-4-trichloroacethlpyrazolone-5 (HPDMCP) as the ligand: Sm(PDMAP)₃·bipy (A₁), Sm(PDMAP)₃·phen (A₂), Sm(PDMCP)₃·bipy(B₁) and Sm(PDMCP)₃·phen (B₂) (Where bipy=2,2′-dipyridyl, phen=1,10-phenanthroline.) were synthesized and identified by elemental analysis. They were characterized by UV and FT-IR spectra analysis. Their luminescence from the solid state were studied. The results show that the fluorescence intensities of B₁ and B₂ are stronger than those of A₁ and A₂, but they all have the same order magnitude. As far as A₁ and A₂, B₁ and B₂ are concerned, both bipy and phen have affect on the fluorescence intensities of the complexes.     

二氰基二硫纶和邻菲罗啉二酮的镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)配合物的合成与性质

The new title complexes ［M(mnt)(phen-5,6-dione)］(M=Ni(Ⅱ)、 Cu(Ⅱ)、 Zn(Ⅱ), mnt=maleonitriledithiolate) are synthesized by reaction of Na₂(mnt) with relevant ［M(phen-5,6-dione)Cl₂］, respectively. The structure and properties of the complexes were characterized by elemental analysis, molar conductivities, TG,IR, UV-Vis, and fluorescence spectra.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

钌(Ⅱ)多吡啶配合物与DNA相互作用的等温滴定量热研究(英)

The interaction of ruthenium(Ⅱ) polypyridyl complex with DNA has been studied by isothermal titration calorimetry (ITC). The results show that complex [Ru(phen)₂PMIP]²⁺ {phen=1,10-phenanthroline, PMIP=2-(4-methylphenyl)imidazo[4,5-f]1,10-phenanthroline} interacts with calf thymus DNA (CT DNA) in terms of a model for a single set of identical sites through intercalation. The results are in agreement with our previous observations from spectroscopic methods and viscosity measurements. In addition, the results further show that the driving force for DNA binding with the complex is mainly driven by the enthalpy changes, and the contribution from the entropy changes to this driving force is negligible.     

三元稀土配合物RE(NTA)2AA的合成、共聚反应性及荧光性能研究

Four new ternary rare earth complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺， Tb³⁺， Dy³⁺) have been synthesized by the reaction of rare earth chloride(RECl₃·6H₂O) with Acrylic Acid (HAA) and 4，4，4-trifluoro-1-(3-pyridyl)-1，3-butanedione(NTA) in alcohol. The copolymerization of the complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺) with methyl methacrylate (MMA) has been studied by 2， 2-azobis-isobutyronitrile as an initiator. Influence of adding Eu(Ⅲ) and 2，2′-bipyridine(bipy) into copolymer Eu(NTA)₂AA-co-MMA on fluorescence property of the Eu copolymer was investigated. The compositions of the complexes and copolymer were characterized by means of elemental analysis and FTIR. The heat decomposing behaviors of the complexes were determined by TG-DTA. The glass transition temperature and molecular weight were obtained by DSC and GPC. The results of fluorescence properties show that the Eu， Sm complexes and Eu copolymer can efficiently emit fluorescence， but the Tb and Dy complexes only emit the fluorescence of β-diketone ligand.     

双核铜(Ⅱ)-氟喹诺酮-邻菲咯啉混配配合物的合成、晶体结构和抗肿瘤活性

A new binuclear copper (Ⅱ) complex with 1,10-phen and fluoroquinolone ligands, [Cu₂(cfc)₂(phen)₂(pip)](NO₃)₂(CO)₂,was synthesized and its crystal structure was solved.The formula of the complex is C₂₈H₂₄ClCuFN₅O₇, and the crystallography data are as follows, triclinic, space group P1, a=0.80372(6)nm, b=0.94712 (7)nm, c=1.67826(13)nm, α=88.5650(10)°, β=80.9920(10)°, γ=70.2780(10)°, V=1.18722(6)nm³, Z=2, D=1.848g· cm^-3, F(000)=676. R₁=0.0627 and wR₂=0.1684 (I>2σ(I)). The copper atom is five- coordinate with square-based pyramidal geometry and involves two nitrogen atoms from phen, two oxygen atoms from cfc and one nitrogen atom from pip anion. The stacking effect between cfc and phen ligands from two neighboring molecules was observed. FT-IR spectrum of the complex was also discussed. Both ligand and complex were assayed against gram-positive and gram-negative bacteria by doubling dilutions method； the complex shows the same mini-mal inhibitory concentration (MIC) as the corresponding ligand against S. Aureus, E. Coli and M. Lutens bac-teria. The inhibitory effect of the ligand and complex on leukemia HL-60 cell line and liver cancer BEL-7402 cell line have been measured by using MTT (Methyl-Thiazol- Tetrozolium) and SRB (Sulphurhodamin B) assay meth-ods, respectively. The results indicated that the complex has strong inhibitory effect on HL-60 and BEL-7402 cell line. CCDC: 203964.     

Two New Copper(Ⅱ) Complexes with p-Cyanobenzoic Acid: Synthesis,Crystal Structures and Properties

The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid(HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA–, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π...π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction(zJ= 0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.     

噻吩甲酰基吡唑啉酮缩乙二胺配合物的合成、表征及生物活性

A new ligand N,N′-bis［(1-phenyl-3-methyl-5-oxo-4-pyrazolinyl)-2-thenoylmethylidyne］ethyl-enediimine (HPMTHP)₂en and its five complexes have been sythesized. These complexes have the general formula ［M(PMTHP)₂en］, where M=Cu(Ⅱ), Ni(Ⅱ)