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=0.1 mo...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=0.1 mol/L, KNO 3; 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.展开更多
Seven novel platinum （Ⅱ） complexes [ Pt（Ⅱ） （NH3） （CH3NH2）X2] （Ⅰ-Ⅶ ） （ X： CH3COO^-, CH2CICOO^- , CHCI2COO^- , C6H5-COO^- , p-CH3O--C6H4-COO^- , p-NH2-C6H4-COO^- , p-NO2--C6H4- COO^-） were prepared and ...Seven novel platinum （Ⅱ） complexes [ Pt（Ⅱ） （NH3） （CH3NH2）X2] （Ⅰ-Ⅶ ） （ X： CH3COO^-, CH2CICOO^- , CHCI2COO^- , C6H5-COO^- , p-CH3O--C6H4-COO^- , p-NH2-C6H4-COO^- , p-NO2--C6H4- COO^-） were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis, IR, UV, and ^1H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence： cisplatin 〉 Ⅳ 〉 Ⅴ 〉 Ⅵ 〉 Ⅶ 〉 Ⅰ 〉 Ⅱ 〉 Ⅲ. Moreover, the complexes （ Ⅰ --Ⅻ） display substantially greater activities agaist EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.展开更多
Two novel mononuclear complexes with 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L）, namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of（5-chloro-quinolin-8-yloxy）acetic acid w...Two novel mononuclear complexes with 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L）, namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of（5-chloro-quinolin-8-yloxy）acetic acid with HgBr2 and CuCl2, respectively. Their structures were characterized by IR, elemental analysis, UV-Vis-NIR spectra, TG and single-crystal X-ray diffraction analysis. Interestingly,（5-chloro-quinolin-8-yloxy）acetic acid is changed as 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L） in complexes 1 and 2. Crystal data for 1： C12H10Br2 Cl Hg NO3, Mr = 612.07, triclinic, space group P1 with a = 8.5983（7）, b = 9.7726（6）, c = 10.1549（6） A, α = 66.355（6）, β = 77.067（8）, γ = 78.803（8）°, V = 756.6（9）A^3, Z = 2, Dc = 2.687 g/cm^3, F（000） = 560, μ = 15.633 mm^-1, R = 0.0351 and w R = 0.0504. Crystal data for 2： C24H20Cl4 Cu N2O6, Mr = 637.76, triclinic, space group P1 with a = 10.5324（9）, b = 11.2377（16）, c = 12.0143（12） ？, α = 83.413（11）, β = 64.475（9）, γ = 83.144（11）°, V = 1270.9（2） ？3, Z = 2, Dc = 1.667 g/cm3, F（000） = 646, μ = 1.324 mm-1, R = 0.0408 and wR = 0.0922. In 1, the HgII centre is a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of L. Intermolecular π-π, C–H…π stacking interactions and intermolecular C–H…Br hydrogen bonds are observed in the molecular packing of 1. In complex 2, each CuII center has a distorted octahedral geometry comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. Intermolecular C–H…Cl hydrogen bonds exist in the molecular packing of 2. The fluorescence emission peak of complexes 1 and 2 appears near 406 and 410 nm, respectively. Optical diffuse-reflection spectral results suggest complex 1 has the property of semiconductor.展开更多
The structure of a binuclear cadmium（Ⅱ） quaternary complex, [Cd2（phen）2- Q2（BP）]n 1 （phen = 1,10-phenanthroline, BP = biphenyl-4,4′-dicarboxylic acid, Q = 8-hydroxy- quinoline-anion）, has been determined by ...The structure of a binuclear cadmium（Ⅱ） quaternary complex, [Cd2（phen）2- Q2（BP）]n 1 （phen = 1,10-phenanthroline, BP = biphenyl-4,4′-dicarboxylic acid, Q = 8-hydroxy- quinoline-anion）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. It crystallizes in the monoclinic system, space group P21/n with a = 13.1906（18）, b = 10.9623（15）, c = 16.947（2）A, β = 111.3430（10）°, V = 2282.5（5）A^3, Z = 4, Mr = 556.85, Dc = 1.620 g/cm^3, F（000） = 1116,μ= 0.994 mm^-1 and S = 1.056. In the structure, 1D chains are connected via biphenyl-4,4′-dicarboxylic acid, 8-hydroxy quinoline anion and binuclear cadmium atoms into an infinite 1-D molecular chain architecture. Via aryl ring π-π stacking interactions a supramolecular structure is formed in 1.展开更多
Two luminescent hetero-trinuclear complexes [Pt2Cu（μ-dpppy）2（C≡CC6H4R-4）4]（Cl O4）（R = H,1;R = CH3,2;dpppy = 2,6-bis（diphenylphosphino）pyridine） have been synthesized and characterized by elemental analyses...Two luminescent hetero-trinuclear complexes [Pt2Cu（μ-dpppy）2（C≡CC6H4R-4）4]（Cl O4）（R = H,1;R = CH3,2;dpppy = 2,6-bis（diphenylphosphino）pyridine） have been synthesized and characterized by elemental analyses,ESI-MS,^1H and ^31P{^1H} NMR spectroscopy,and X-ray crystallography for 2.Their photophysical properties in the solid state and in solutions at room temperature and in frozen glasses at 77 K were studied.Both complexes 1 and 2 show strong orange-red emission in the solid state at room temperature and in frozen glasses at 77 K,and weak emission in solutions.展开更多
基金Supported by the Foundation of Academ y L eader of Zhejiang Gongshang U niversity(No.19972 0 0 2 )
文摘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=0.1 mol/L, KNO 3; 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.
文摘Seven novel platinum （Ⅱ） complexes [ Pt（Ⅱ） （NH3） （CH3NH2）X2] （Ⅰ-Ⅶ ） （ X： CH3COO^-, CH2CICOO^- , CHCI2COO^- , C6H5-COO^- , p-CH3O--C6H4-COO^- , p-NH2-C6H4-COO^- , p-NO2--C6H4- COO^-） were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis, IR, UV, and ^1H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence： cisplatin 〉 Ⅳ 〉 Ⅴ 〉 Ⅵ 〉 Ⅶ 〉 Ⅰ 〉 Ⅱ 〉 Ⅲ. Moreover, the complexes （ Ⅰ --Ⅻ） display substantially greater activities agaist EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.
基金Supported by Key Laboratory of Organic Synthesis of Jiangsu Province(KJS1308)
文摘Two novel mononuclear complexes with 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L）, namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of（5-chloro-quinolin-8-yloxy）acetic acid with HgBr2 and CuCl2, respectively. Their structures were characterized by IR, elemental analysis, UV-Vis-NIR spectra, TG and single-crystal X-ray diffraction analysis. Interestingly,（5-chloro-quinolin-8-yloxy）acetic acid is changed as 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L） in complexes 1 and 2. Crystal data for 1： C12H10Br2 Cl Hg NO3, Mr = 612.07, triclinic, space group P1 with a = 8.5983（7）, b = 9.7726（6）, c = 10.1549（6） A, α = 66.355（6）, β = 77.067（8）, γ = 78.803（8）°, V = 756.6（9）A^3, Z = 2, Dc = 2.687 g/cm^3, F（000） = 560, μ = 15.633 mm^-1, R = 0.0351 and w R = 0.0504. Crystal data for 2： C24H20Cl4 Cu N2O6, Mr = 637.76, triclinic, space group P1 with a = 10.5324（9）, b = 11.2377（16）, c = 12.0143（12） ？, α = 83.413（11）, β = 64.475（9）, γ = 83.144（11）°, V = 1270.9（2） ？3, Z = 2, Dc = 1.667 g/cm3, F（000） = 646, μ = 1.324 mm-1, R = 0.0408 and wR = 0.0922. In 1, the HgII centre is a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of L. Intermolecular π-π, C–H…π stacking interactions and intermolecular C–H…Br hydrogen bonds are observed in the molecular packing of 1. In complex 2, each CuII center has a distorted octahedral geometry comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. Intermolecular C–H…Cl hydrogen bonds exist in the molecular packing of 2. The fluorescence emission peak of complexes 1 and 2 appears near 406 and 410 nm, respectively. Optical diffuse-reflection spectral results suggest complex 1 has the property of semiconductor.
基金Siping Sci-tech Development Planning Project(No.2005012)
文摘The structure of a binuclear cadmium（Ⅱ） quaternary complex, [Cd2（phen）2- Q2（BP）]n 1 （phen = 1,10-phenanthroline, BP = biphenyl-4,4′-dicarboxylic acid, Q = 8-hydroxy- quinoline-anion）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. It crystallizes in the monoclinic system, space group P21/n with a = 13.1906（18）, b = 10.9623（15）, c = 16.947（2）A, β = 111.3430（10）°, V = 2282.5（5）A^3, Z = 4, Mr = 556.85, Dc = 1.620 g/cm^3, F（000） = 1116,μ= 0.994 mm^-1 and S = 1.056. In the structure, 1D chains are connected via biphenyl-4,4′-dicarboxylic acid, 8-hydroxy quinoline anion and binuclear cadmium atoms into an infinite 1-D molecular chain architecture. Via aryl ring π-π stacking interactions a supramolecular structure is formed in 1.
基金Supported by NSF of Fujian Province(No.2014J01046)Key Science Project(type A)of the Fujian Provincial Department of Education,China(No.JA12021)the NSF for Fostering Talents in Basic Research of China(No.J1103303)
文摘Two luminescent hetero-trinuclear complexes [Pt2Cu（μ-dpppy）2（C≡CC6H4R-4）4]（Cl O4）（R = H,1;R = CH3,2;dpppy = 2,6-bis（diphenylphosphino）pyridine） have been synthesized and characterized by elemental analyses,ESI-MS,^1H and ^31P{^1H} NMR spectroscopy,and X-ray crystallography for 2.Their photophysical properties in the solid state and in solutions at room temperature and in frozen glasses at 77 K were studied.Both complexes 1 and 2 show strong orange-red emission in the solid state at room temperature and in frozen glasses at 77 K,and weak emission in solutions.
基金supported by the National Natural Science Foundation of China(21073143)“Chunhui Project”from the Ministry of Education of China(Z2009-1-71002,Z2009-1-71006)+2 种基金Graduate Starting Seed Fund of Northwestern Polytechnical University(NPU),China(Z2015152)NPU Foundation for Graduate InnovationChina~~
