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.     

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.     

配合物稳定性与酸碱强度之间的直线自由能关系——ⅪⅤ.N-(取代苯基)亚氨基二乙酸与铜(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)钴(Ⅱ)二元配合物的稳定性研究

The dissociation constants of N-(para-substituted phenyl) iminodiacetic acid (p-RPhID A, R= Cl, H, CH₃, CH₃O) and N-(ortho-substituted phenyl) iminodiacetic acid (o-RPhlDA) and the formation constants of binary complex compounds of Cu(Ⅱ)-o-RPhIDA, Cu(Ⅱ)-p-RPhIDA, Co(Ⅱ)-p-RPhIDA, Ni(Ⅱ)-p-RPhIDA and Zn(Ⅱ)-p-RPhIDA were determined by pH method in the presence 0.1mol·dm^-3KNO₃ at 25℃ . It has been found that linear free energy relationships not only exist between stability of these binary complex compounds and base strength of ligand, but also exist between logβ and σ'(=pK₂-pK₂).The deviation of Cu(Ⅱ)-o-CH₃PhIDA from linearity may be ascribed to steric effect of methyl group at ortho position.     

锌(Ⅱ)-氨基酸水杨醛席夫碱-α-氨基酸三元配合物的稳定性

The stability constants of binary complexes of Zn(Ⅱ)-α-amino acid and ternary complexes of Zn(Ⅱ)-N-Salicylideneaminio acid (ligand A)-α-amino acid(ligand B) at (25±0.1)℃ and in the presence of 0.1 mol·L^-1 KNO₃ have been determined by pH method. The α-amino acid(Aa) used were Glycine(Gly), L-Serine(Ser), L-Leucine(Leu), L-Proline(Pro) and L-Phenylalanine(Phe). It was found that the linear free energy relationship (LFER) exists nicely between the following parameter pairs logβ₁₀₂ and pK^B₂, logβ₁₁₁ and pK^B₂, and logβ₁₁₁ and pK^A₂. The ΔlgK was used to characterize the stability of ternary complexes related to the stability of parent binary complexes. The hydrophobic interaction between ligands in the ternary complexes was studied.     

铕(Ⅲ)-锌(Ⅱ)双核配合物的合成和表征

Two new Eu(Ⅲ)-Zn(Ⅱ) binuclear complexes Zn(Salen)EuL₃ have been synthesized, where Salen=Shiff base of bissalicylaldehyde with ethlenediamine and L=acetylacetone (for complex Ⅰ) or trifluoroacetylacetone (for compelx Ⅱ). Analytical experimetal such as IR, UV and elemental analysis suggest the possible component and structure, the fluorescence spectrum of the complex Ⅱ suggests the M^*→M fluorescence mechanism.     

草酸根桥联的双核铜(Ⅱ)配合物[Cu2(phen)2(H2O)2(μ2-C2O4)](NO3)2的合成及晶体结构

A new binuclear copper(Ⅱ) complex, [Cu₂(phen)₂(H₂O)₂(μ₂-C₂O₄)](NO₃)₂, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P2₁/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm³, D_c=1.769 Mg·m^-3, Z=2, F(000)=744, R₁=0.025 4, wR₂=0.069 5, Gof=1.077, Δρ=328～-455 e·nm^-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO₃^- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO₃^- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.     

超分子钴(Ⅱ)配合物[CoL(H2O)2]n的合成与结构表征

A mononuclear Cobalt(Ⅱ) complex [CoL(H₂O)₂]_n (H₂L: 4,4′,6,6′-Tetrabromo-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol), has been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction single crystal structure analysis. The crystal of the complex belongs to monoclinic space group P2₁/c with a=2.516 8(3) nm, b=1.023 43(18) nm, c=0.789 17(14) nm, β=91.375(2)°, V=2.032 1(5) nm³, Z=4, D_c=2.317 Mg·m^-3, μ(Mo Kα)=8.747 mm^-1, F(000)=1 356, R₁=0.049 7, wR₂=0.110 4. The crystal structure of [CoL(H₂O)₂]_n indicates that the complex consists of one cobalt(Ⅱ) atom, one L^2- unit and two coordinated water molecules, and the coordination number of the cobalt(Ⅱ) atom is six. One-dimensional chain supramolecular structure is formed by intermolecular hydrogen bonds and π-π stacking of neighboring benzene rings. CCDC: 652649.     

配位聚合物{[CoL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成、波谱表征和磁学性质

A new Schiff base complex， CoL(ClO₄)·3H₂O (1) {L represents condensed from equal molar ratio of sali-cylaldehyde and diethylenetriamine} was synthesized and characterized. Further， a new coordination polymer， {[CoL][Fe^ⅡFe^Ⅲ(ox)₃·1.5H₂O]}_∞ (2)， was synthesized and characterized， where ox^2-=oxalate. The results of the IR and M?ssbauer spectra of 2 revealed that the coordination polymer exists 2-D layer structure in the solid state， and anions layer was formed by [^ⅡFe^Ⅲ(ox)₃]^- unit. The magnetic properties of 2 have been measured and the results indicate that there is magnetic ordering in the low temperature， which may arise from intermolecular ferromagnetic interactions or spin canted effects.     

壳聚糖/Pb(Ⅱ)模板壳聚糖膜与Pb(Ⅱ)螯合反应的动力学及机理探讨

Chitosan and chitosan membranes with Pb(Ⅱ) ion as template were studied. The adsorption isotherms were correlated by dc/dt=-kcⁿ at the temperature of 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃. By means of linear correlation, the shapes of the isotherm curves were similar to the kinetic function of 2/c^1/2=-kt and the apparent activation energy for with chitosan(123.8 kJ·moL^-1) was larger than that of membrane with Pb(Ⅱ) ion(92.3kJ·moL^-1). The chitosan membrane with Pb(Ⅱ) ion template was better “memory” function. The adsorption mechanism of chitosan with Pb(Ⅱ) was studied by IR and XPS. The results indicated that the nitrogen in -NH₂ and the oxygen in C₃-OH of chitosan were coordination atoms.     

2′-(4-氟基苯亚甲基)-3，5-二羟基苯甲酰腙Ni(Ⅱ)配合物的合成、表征、晶体结构及光谱性质

In ethanol, a new mononuclear nickel(Ⅱ) complex incorporating Schiff base ligands, [NiL₂](DMF)₄ (HL=2′-(4-fluorobenzylidene)-3,5-dihydroxybenzoylhy drazide) has been synthesized and characterized by IR, UV-Vis, elemental analysis and X-ray crystal structure analysis. The single crystal structure has been determined by single-crystal X-ray diffraction structure analysis. The crystal belongs to monoclinic system, space group P2₁/c with a=1.617 3(2) nm,b=1.798 5(2) nm, c=0.737 61(10) nm, β=91.953(3)°, V=2.144 3(5) nm³, Z=2, μ=0.526 mm^-1, D_c=1.390 g·cm^-3, F(000)=940, R_int=0.105 3. In the compound nickel(Ⅱ) atom is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. The complex has the centrosymmetry and the nickel(Ⅱ) ion is located in the center. CCDC: 675522.     

三维网状的4-羧基苯氧乙酸锶(Ⅱ)配位聚合物[Sr2(4-CPOA)2(H2O)5]n的合成、结构与热稳定性研究

A novel coordination polymer of [Sr₂(4-CPOA)₂(H₂O)₅]_n (where 4-CPOA^2- is 4-carboxylphenoxyacetate) has been synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex belongs to monoclinic system with space group C2/c, a=2.563 9(5) nm, b=1.162 7(2) nm, c=0.742 96(15) nm, β=99.64(3)°. V=2.183 5(7) nm³, Z=4, M_r=653.60, D_c=1.988 g·cm^-3, R=0.027 8, wR=0.058 1. The strontium atom has a bicapped triangular prismatic coordination geometry, involving four oxoacetate oxygen atoms, one ether oxygen atom from different 4-CPOA^2- ligands and three water molecules. The strontium(Ⅱ) ions are linked by 4-CPOA^2- ligands and water molecules to form a 3D network structure. CCDC: 223313.     

一维聚合物{[Co(N3)2(dps)2]·0.5H2O}n的合成，结构和磁性质

A coordination polymer {[Co(N₃)₂(dps)₂]·0.5H₂O}_n (1) (dps=dipyridin-4-ylsulfane) with one dimensional chains has been synthesized and the structure and magnetic properties were characterized. Complex 1 crystallizes belongs to monoclinic system and has space group P2₁/c. The Co^Ⅱ ion is six-coordinated and located at a compressed octahedral environment due to the Jahn-Teller effect. The ligand of dps bridges between Co^Ⅱ ions producing the infinite chains of Co…Co along a direction and, interestingly, four pyridyl groups of dps ligands form a propeller-shaped coordination geometry around Co^Ⅱ ion with the same spiral within the chain. These 1D chains are further linked through the hydrogen bonds to generate a 3D supermolecular network. Magnetic studies indicated that complex 1 shows very weak antiferromagnetic coupling between Co^Ⅱ ions in low temperature. CCDC: 769596.     

Ni(Ⅱ)与Hbbimp配合物的合成、表征及晶体结构

A new complex with binuclear nickel(Ⅱ) complex [Ni₂(bbimp)(CH₃CH₂OH)₂Cl₂]Cl·4H₂O (bbimp=2，6-bis[bis(2-benzimidazolylmethyl)]aminomethyl-4-methylpheno)(o)had been synthesized and characterized by ele-mentary analysis， IR and UV. The molecular structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is monoclinic， space group P2₁/n with a=20.803(2)?， b=30.708(3)?， c=20.959(2)?， β=105.776(2)°， Z=8， V=12885(2)?³， D_x=1.132Mg·m^-3， μ=0.755mm^-1， F(000)=4592， R₁=0.1267， S=1.376. It was showed that the nickel(Ⅱ) cation is the central ion of a distorted octahedral coordination with two N belonging to benzimidazole， a bridging phenolate O， a N of tertiary amine， a Cl anion， and an O of an ethanol molecule. Two nickel(Ⅱ) cations in a molecular structure had the same coordinated environment. CCDC： 197601.     

二重穿插锰配合物Mn2(ADB)2(DMSO)4DMSO的溶剂热合成和结构研究

A novel Mn coordination polymers, Mn₂(ADB)₂(DMSO)₄·DMSO (H₂ADB=4,4′-azodibenzoic acid), has been prepared by solvothermal reaction and characterized by element analysis, IR spectra and single-crystal X-ray diffraction. The crystallographic data shows that the title complex crystallizes in monoclinic space group C2/c. Each Mn(Ⅱ) is six-coordinated to four O atoms from three ADB^2- ligands, two oxygen atoms from two DMSO molecule and forms distorted octahedral coordination geometry. The Mn(Ⅱ) dimers by the carboxyl groups of the ADB^2- ligands were interlinked together by the different carboxylate coordination modes of ADB^2- ligands, to yield scaffolds with 2D network with 4.8² topological structures. CCDC: 745678.     

肉桂醛水杨酰腙Ni(Ⅱ)配合物的合成﹑晶体结构、抑菌活性及电化学性质

A ligand cinnamaldehyde salicylhydrazone(C₁₆H₁₄N₂O₂, HL) and its Ni(Ⅱ) complex, [NiL₂(DMF)₂]·(DMF)₂ have been synthesized and its ingredients, structure and Electrochemical Properties were characterized by the element analysis, IR spectrum, X-ray single crystal diffraction structural analysis and cyclic voltammetry, respectively. The complex crystallizes in monoclinic, space group P2₁/n with cell parameter a=11.160 1(12) nm, b=18.919(2) nm, c=11.997 4(13) nm, β=115.694(2)°, and V=2 282.7(4) nm³, Z=2, D_c=1.289 g·cm^-3. The crystal structure reveals that the center nickel(Ⅱ) cation is bonded to two ligands and two solvent DMF molecules to form an octahedral coordination geometry. The bioactivity test shows that the Ni(Ⅱ) complex of cinnamaldehyde salicylhydrazone has selective antibacterial property against S. Aureus and B. Subtilis. CCDC: 722241.     

异核配合物[Co(Ⅲ)(Hdmg)2(H2O)2Mn(Ⅱ)Cl3]的合成与晶体结构

A new coordination compound Co(Ⅲ)(Hdmg)₂(H₂O)₂Mn(Ⅱ)Cl₃ was synthesized and its crystal structure was determined. The crystal data are as follows: crystal system, orthorhombic; space group, C222₁(#20); a=1.18315(3) nm, b=1.28631(5) nm, c=1.14355(2) nm, V=1.74037(9) nm³, Z=4, D_c=1.857 g·cm^-3, F(000)=980.00, μ(MoKα)=21.69 cm^-1, R₁=0.030, wR₂=0.92. The coordination geometries around Co(Ⅲ) and Mn(Ⅱ) atoms are distorted octahedral and distorted trigonal bipyramidal, respectively. The Hdmg chelates Co(Ⅲ) and bridges to two Mn(Ⅱ) atoms to form a polyheteronuclear helical structure along the c axis.     

Cu(Ⅱ)-2′-(2-噻吩亚甲基)水杨酰腙Schiff碱配合物的合成、表征、晶体结构及抑菌活性研究

In ethanol, the copper(Ⅱ) complex with the 2′-(2-thienylidene)-h ydroxybenzoylhydrazide, Cu(C₁₂H₁₀N₂O₂S)₂, was synthesized, and it′s structure was characterized by IR, UV and elemental analysis. The single crystal structure has been determined by X-ray diffraction analysis. The crystal belongs to monoclinic system, space group C2/c with cell constants, a=2.273 6(4) nm, b=0.592 12(9) nm, c=1.828 1(3) nm, β=109.735(5)°, V=2.316 4(7) nm³, Z=4, μ=1.164 mm^-1, D_c=1.595 g·cm^-3, F(000)=1 140, R=0.048 6, wR=0.101 6. In the compound copper(Ⅱ) atom is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. Their biological activities have been measused. The results show that the anti-bacterial activity of the coordination compound is much better that of the ligand. CCDC: 272938.     

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.     

新型一维Cd(Ⅱ)配位聚合物的合成、晶体结构和光致发光性质

A new 1D chain coordination polymer [Cd(dpq)(ox)_0.5Cl]_n(1) (dpq=dipyrido[3,2-d:2′,3′-f]quinoxaline and ox=oxalate) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and single crystal X-ray diffraction analysis. Compound 1 (CdClC₁₅H₈N₄O₂): monoclinic, space group P2₁/c, a=0.854 04(5) nm, b=2.094 90(13) nm, c=0.839 22(5) nm, Z=4, V=1.438(15) nm³, M_r=424.11, D_c=1.959 g·cm^-3, F(000)=828.0, μ=1.719 mm^-1, S=1.028, the final R=0.025 8 and wR=0.057 5. The crystal structure analysis indicates that the cadmium ion is coordinated by two oxygen atoms from a oxalate, two chelating nitrogen atoms from a dpq molecule and two Cl^- anions. The adjacent Cd(Ⅱ) ions are linked by Cl^- anions and oxalate ligands in alternate sequence to form a 1D chain coordination polymer and the adjacent chains are further connected by π-π stacking interactions to form a 2D supramolecular network. Moreover, the title compound exhibits blue emission in the solid state at room temperature. CCDC: 680748.     

一个新的双核锌配合物Zn2(dhaash)2(py)4的合成及晶体结构

The crystal of binuclear zinc complex Zn₂(dhaash)₂(py)₄ was obtained in DMF and pyridine, where H₂dhaash is 2,4-dihydroxy-5-acetylacetophenone-N-salicylhydrazone. It has been characterized by IR, UV, element analysis and X-ray single crystal diffraction. The crystallographic data were as follows: monoclinic system, space group P2₁/c, a=1.108 98(11) nm, b=1.640 84(16) nm, c=1.445 14(14) nm, β=108.617(2)°, Z=2, V=2.492 1(4) nm³, D_c=1.466 g·cm^-3, M_r=1 099.74, μ=1.031 mm^-1, F(000)=1 136 and the final R=0.044 8 and wR=0.105 8 for 4 143 observed reflections with I≥2σ(I), respectively. The X-ray crystal structure analysis revealed that, in the centrosymmetric binuclear complex molecule, two zinc(Ⅱ) centers are linked by two oxygen atoms (O(3) and O(3A)), respectively. Zn(1)…Zn(1A) distance is 0.314 81(6) nm, O(3)…O(3A) distance is 0.270 4(2) nm. Every zinc(Ⅱ) ion has an elongated octahedral coordination. For example, the two pyridine nitrogen atoms, one oxygen atom and one nitrogen atom from salicylhydrazone, one oxygen atom from 2,4-dihydroxy-5-acetylacetophenone in one dhaash^2- ligand and one oxygen atom from 2,4-dihydroxy-5-acetylacetophenone in another dhaash^2- ligand coordinated to zinc(Ⅱ) ion, respectively. Two zinc(Ⅱ) ions and all the 72 non-hydrogen atoms in the two dhaash^2- ligands are in the same plane. CCDC: 261929.