6′，6″-二吡啶基-2，2′：4′，4″：2″，2′′′-四联吡啶稀土配合物的合成、表征及荧光性质研究(英)

Two series of solid complexes of rare earth nitrates and picrates with the “back-to-back” terpyridine, 6′,6″-bis(2-pyridyl)-2,2′:4′,4″:2″,2′′′-quaterpyridine (L) have been synthesized. These complexes have been characterized by elemental analysis, conductivity measurements, thermal analysis and IR spectroscopy. At the same time, the luminescent properties of the Eu(Ⅲ) and Tb(Ⅲ) complexes were also studied.     

以冠醚为骨架的多足配体稀土配合物的合成、表征及荧光性质研究

A novel podand ligand using crown ether as skeleton and N-benzylsalicylamide as functional arms, 4,5-bi{2′-methylbenzeneaminoformyl)phenoxyl]methyl}-benzo-12-crown-4 (L), and its rare earth nitrate complexes have been synthesized. These complexes were characterized by elemental analysis, conductivity measurements and IR spectroscopy. Spectrographic analyses suggest that the complexes show a similar coordination mode. At the same time, the luminescent properties of the Eu(Ⅲ) and Tb(Ⅲ) complexes were also studied.     

Bond Valence Sum Analysis of Tl（Ⅰ） and Tl（Ⅲ） Complexes with O and N Donors

The influence of the lone pair of electrons in thallium complexes is analyzed using the bond valence sum method.Bond length data for metal-organic Tl complexes were obtained from the Cambridge Structural Database(CSD),and problems with searching the CSD file for Tl complexes are discussed.The recommended R0 values for Tl(Ⅰ)-O of 2.162 ,Tl(Ⅲ)-O of 2.016 ,Tl(Ⅰ)-N of 2.286 ?,and for Tl(Ⅲ)-N of 2.014  used with b = 0.37 were derived from analyses of homoleptic Tl-O,Tl-N,and heteroleptic Tl-O and-N metal organic complexes.These R0 values can be used to assign correctly the oxidation state of Tl in complexes containing any combination of Tl-O or Tl-N bonds.Examples of questionable oxidation states for Tl complexes are given.The R0 value for Tl(Ⅲ)-Cl of 2.300  was also determined.     

5,10,15,20-Tetrakis （p-4-fluorobenzoyloxy） phenyl Porphyrin and Its Transition Metal Complexes

The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10,15,20-tetrakis(p-4-fluorobenzoyloxy) phenyl porphyrin(TFBOPPH2) and its transition metal complexes {TFBOPPM [M=Mn(Ⅲ), Fe(Ⅲ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ)]} were synthesized and characterized by means of UV-Vis, IR photoacoustic spectrometry, 1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrin molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balanceable anion in Fe(Ⅲ) and Mn(Ⅲ) complexes.     

Thermal Behavior and Decomposition Kinetics of the Complexes of CuX2 （X=NO3, Br, CI and CIO4） with 3,3＇-Dimethyl-1 -（1 H-1,2,4-triazol-1-yl）-2-butanone

The thermal behaviors of the complexes of Cu(DMTZB)4X2 (DMTZB=3,3‘-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, X=NO3 or ClO4) and Cu(DMTZB)2 X2 (X=Br or Cl) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC, EDS and elemental analysis techniques. The resuits showed that their decomposition proceeded in three different ways mainly depending on the anions in the molecules. The heat effect associated with the decomposition step of DMTZB molecules was also different. The decomposition mechanisms and the kinetic parameters of DMTZB were determined and calculated by jointly using four methods, which showed that its pyrolysis was controlled by D3 mechanism but with different activation energies and pre-exponential factors for different complexes.     

水杨醛缩2-氨基-4-苯基噻唑及其配合物的合成与仿酶催化活性研究

The new containing Surfur Schiff base Salicylaldelye-2-amino-4-Phenylthiazole(SAPTZ) and its Cu(Ⅱ)、Zn(Ⅱ)、Ni(Ⅱ) and Co(Ⅱ) compelexes were synthesized. The structures of the complexes were characterized by elemental analysis, IR and UV-vis. The peroxidase-like activity of the complexes for the oxidation of Vc with H₂O₂ was determined.     

Synthesis, Characterization, Spectroscopy and Study of Antimicrobial Properties of Two New Substituted Trichloroaluminate（Ⅲ） Complexes [AlCl3X]- （X = SCN-, CN-）

The synthesis and characterization of two new aluminate(Ⅲ) complexes with general formula K[AlCl3X] are reported. These compounds derived from aluminate trichloride and related salts. Potassium trichlorothiocyanoaluminate, PCTA, and potassium trichlorocyanatoalu-minate, PCCA, are two new ionic aluminate complexes. They can be easily synthesized in a nearly quantitative yield by using the direct reaction of AlCl3 and KX. The complexes were characterized by physico-chemical and spectroscopic methods. Theoretical calculations have been used for the extraction of structural and spectroscopic data of these new synthesized complexes. The antibacterial activities of such compounds were studied against the Staphylococcus aureus, Escherichia coli, Staphylococcus Epidermidis, Estreptococo B and Shigella.     

Crystal Structures of Urokinase-type Plasminogen Activator in Complex with 4-（Aminomethyl） Benzoic Acid and 4-（Aminomethyl-phenyl）-methanol

Urokinase-type plasminogen activator （uPA） is a trypsin-like serine protease and plays a key role in several biological processes, including tissue remodeling, cell migration, and matrix degradation. The inhibitors of uPA have been shown to prevent the spread of metastasis and tumor growth, and accordingly uPA is widely recognized as a target for the treatment of cancer. In this work, we report the crystal structures of the complexes of uPA with its inhibitors： 4- （aminomethyl）-benzoic acid （AMBA） and 4-（aminomethyl-phenyl）-methanol （AMPM）, both at a resolution of 2.35 А. The inhibitory constants of these two inhibitors were measured by a chromogenic competitive assay, and it was found that AMBA is a better inhibitor for uPA （Ki = 2.68 mM） than AMPM （Ki = 13.99 mM）. The structural study shows that the binding mode of inhibitor AMBA on uPA is similar to that of AMPM on uPA, both docked into the active site S1 pocket of uPA. Structural details of these complexes are provided to explain the difference of inhibitory constants.     

稀土与β-二酮及2-（2-吡啶）苯并咪唑三元配合物的研究

As useful fluorescent reagent, rare earth complexes with β-diketones have been　extensively studied. Four new rare earth (La, Eu) ternary complexes with　β-diketones, (benzoylacetone (Hbza), 2-thenoyltrifluoroacetone, (HTTA)) and organic base (2-(2-pyridyl) benzimidazole, (Hpbi)) have been synthesized and characterized by elemental analysis, IR, NMR. The general formulae of these complexes are ［Ln(bza)₃(Hpbi)］ and［Ln(TTA)₃(Hpbi)］. The effects of coordinated base on UV, especially on fluorescent properties of the complexes were discussed. The results showed that the dehydro-Hpbi, pbi^{－, strongly enhances the fluorescence of the complexes.}     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

The Study on the Stability Constant and Species Distribution of Eu （Ⅲ） and Tb （Ⅲ） Complexes with BDBPH

The stability constants and species distributions of complexes of two lanthanide ions, Eu（Ⅲ） and Tb（Ⅲ）, with a macrocyclic ligand, BDBPH, in 1：1 and 2：lsystem, were determined potentiometrically at 25.0 ℃ and I=0.100 mol L^-l. The two metal ions could form deprotonated mono- or dinuclear complexes with BDBPH after the first two protons of the ligand completely neutralized. At higher pH values, Eu（Ⅲ） could not form hydroxy complexes with BDBPH, while Tb（Ⅲ） could form hydroxy complexes in the type of M2L（OH）, M2L（OH）2, and M2L（OH）3.     

Synthesis, Characterization, Spectroscopic and Electrochemical Properties of New Mono- and Binuclear Copper（Ⅰ） Complexes with Substituted 2,2′-Bipyridine

The mono- and binuclear Cu(Ⅰ) complexes with substituted 2,2′-bipyridine and iodide ligands, [CuL2]BF4(L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2′-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2′-bipyridine (b) and 6-(4-methoxylphenyl)-2,2′-bipyridine (c)) and [Cu2(μ-I)2L2] were prepared, and the crystal structures of the complexes were obtained from signal-crystal X-ray diffractional analysis. The spectroscopic properties of the complexes in dichloromethane are dominated by low energy MLCT bands from 360 to 650 nrn. The electrochemical studies of mononuclear complexes reveal that the complexes have stable copper(Ⅰ) state.     

双(3-对甲苯基-2-硫代咪唑-1-基)-(3-甲基-5-苯基吡唑-1-基)硼氢酸根的镉及钴配合物的合成与结构表征

Two new complexes CdL₂ (1) and CoL₂ (2) were synthesized by reactions of L {L =hydro[bis(3-p-tolyl-2-thioimidazol-1-yl)-(3-phenyl-5-methyl-pyrazol-1-yl)]borate} with cadmium(Ⅱ) and cobalt(Ⅱ) acetate respectively, and structurally characterized. The title complexes feature distorted trigonal dipyramidal geometries with a S₄H donor set defined by the sulphur and hydrogen atoms of two tripodal sulfur-rich ligands. CCDC: 235514, 1; 244021, 2.     

Preparation,Characterization and Properties of Two New Lanthanide(Ⅲ)-5-(2-pyridyl)tetrazolate Complexes

Two new mononuclear lanthanide(Ⅲ) complexes Ln(pytz)3(H2O)3·(H2O)3.5[Ln=Tb(1);Eu(2);Hpytz=5-(2-pyridyl)tetrazole] were synthesized by reacting Hpytz with the corresponding lanthanide(Ⅲ) ions and characterized.The single crystal X-ray diffraction analysis reveals that complexes 1 and 2 are isostructural and the lanthanide(Ⅲ) ions in both complexes 1 and 2 are nine-coordinated,with three oxygen atoms of three coordination water molecules and six nitrogen atoms of three pytz ligands,forming a monocapped square antiprism.Extensive hydrogen bonds exist,resulting in a three-dimensional supramolecular network structure by hydrogen-bonds in both complexes 1 and 2,respectively.Complex 1 exhibits typical green fluorescence of Tb(Ⅲ) ion and complex 2 red fluorescence of Eu(Ⅲ) ion,in solid state at room temperature.     

Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum（Ⅱ） Complexes

The stability constants of some ternary mixed-ligand complexes, Pt (Phen)(CA) , where Phen-1,10-phenanthroline and CA^-=carboxylate, were determined by means of potentiometric pH titration in aqueous solutions (I=0. 1mol/L, KNO3; 25℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands (PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen) (PCA)^- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.     

Synthesis and Magnetic Properties of Fe（Ⅱ） and Nd（Ⅲ） Complexes of Poly（N-2-thiazolylacrylamide）

N-2-Thiazolylacrylamide （NTA） was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the corresponding metal complexes with higher loads easily. FTIR, ^1H NMR, elemental analysis, and energy-dispersive X-Ray spectroscopy （EDX） were applied to characterize these materials. The magnetic behavior of Fe（Ⅱ） and Nd（Ⅲ） complexes of poly（N-2-thiazolylacrylamide） was examined by a PPMS-9T magnetometer, exhibiting the characteristics of a soft ferromagnet. It is found that the Nd（Ⅲ） complex has an extremely high relative saturation magnetization of 35 emu/g.     

Synthesis and Crystal Structure of Potassium triaqua（ethyleneamin—N,N,N‘,N’—tetraacetate）gadolinium（Ⅲ）pentahydrate

1 INTRODUCTION The chemistry of lanthanide (Ⅲ) complexes has a considerable history. The stereochemistry of the lanthanide (Ⅲ) complexes with ethyleneamine- N, N, N, N-tetraacetate (Edta) has been investigated[1~10]. Up to now, many Ln-Edta complexes with the chemical formulae of M[Ln(Edta)(H2O)m]nH2O (M = Na+, K+, Cs+, NH4+, Guanium; m = 2, 3; n = 0, 1, 3, 5) have been reported and suggested that the coordination modes and crystal systems for the Ln-Edta complexes depend on …     

Synthesis and Characterization of New Macrocyclic Cu（Ⅱ） Complexes from Various Diamines, Copper（Ⅱ） Nitrate and 1,4-Bis（2-formylphenoxy）butane

Six new macrocyclic complexes were synthesized by a template reaction of 1,4-bis（2-formylphenoxy）butane with diamines and Cu（NO3）2·3H2O and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra. The metal to ligand molar ratios of the Cu（Ⅱ） complexes were found to be 1 ： 1. The Cu（Ⅱ） complexes are 1 ： 2 electrolytes as shown by their molar conductivities （∧m） in DMF at 10^-3 mol·L^-1. Due to the existence of free ions the Cu（Ⅱ） complexes are electrically conductive. Their configurations were proposed to be probably distorted octahedral.     

The Synthesis of Glycosyl Phosphite-Pt（Ⅱ） Complexes

Ethylene glycol phosphorochloridite 1 or catechol phosphorochloridite 2 reacted with isopropylidene derivatives of D-glucose, D-galactose, D-mannose and D-fructose, a series of glycosyl phosphites were obtained. These glycosyl phosphites form optically active complexes with simple Pt (Ⅱ) salts. Pt (Ⅱ) is coordinated to the phosphorus atom, most of the metal complexes are quite stable.     

Interactions with ATP, DNA Cleavage and Anti-tumor Activities of Complexes with Anions [Mo（V）O2（O2CeH4）2]^3-, [Mo（Ⅴ）0.5W（Ⅵ）0.5O2（O2C6H4）2]^2.5- and [W（Ⅵ）O2（O2C6H4）2]^2-

(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands.