Time-resolved fluorescence spectra of europium methylbenzoates (MBA)with 1,10-phenanthroline(phen)have been measured at room temperature.For each of the europium chelates,where the ligand triple states lie above the ~...Time-resolved fluorescence spectra of europium methylbenzoates (MBA)with 1,10-phenanthroline(phen)have been measured at room temperature.For each of the europium chelates,where the ligand triple states lie above the ~5D_1 level of Eu^(3-),the spectra providc evidence that the Eu^(3-) ~5D_0 state is populated by nonradiative energy transfer from the higher-lying ~5D_1,state.The relaxation time for energy decay from ~5D_1 state is measured in the microcrystals to bc of the order of a few microseconds.It is suggested that the ligand C=0 and C=C stretching vibrations and Eu-O vibrations,chclate ring and benzene ring vibrations make important contributions to the relaxation process.The ~5D\-1—~5D\-0 relaxation time of Eu- (p-MBA)_3phen is shorter than those of Eu(m-MBA)_3phen and Eu(o-MBA)_3phen since nonradiative degradation to ~5D_0 from ~5D_1 appears to be more strongly influenced by the E_u^(3+)sites in the former.展开更多
The complex Eu(IB)_3(phen)·2H_2O was synthesized. The results show that the strong fluorescence emitting of 593 and 615 nm for Eu^(3+) in the Eu(IB)_3(phen) complex is related to the transitions (()~5D_0-()~7F_1)...The complex Eu(IB)_3(phen)·2H_2O was synthesized. The results show that the strong fluorescence emitting of 593 and 615 nm for Eu^(3+) in the Eu(IB)_3(phen) complex is related to the transitions (()~5D_0-()~7F_1) and (()~5D_0-()~7F_2,) respectively. A sensitive method for the determination of adenosine disodium triphosphate (ATP) by fluorescence quenching is proposed. The method is based on the ability of ATP to inhibit the formation of a strong fluorescent complex of Eu(IB)_3(phen). In conditions of pH 6.7 HAc-NaAc buffer, λ_(ex)=273 nm and λ_(em)=615 nm, the linear range of the determination was 0.1～10 μg·ml^(-1) and the detection limit was 0.03 μg·ml^(-1) for ATP. The method has been applied to determine ATP in adenosine disodium triphosphate tablets samples with relative standard deviation of 2.18% and recovery of (98.4%～)104.0%.展开更多
The complex of Eu 3+ and Enoxacin(ENX) and Phen was synthesized. Its compositions is Eu(ENX)_3(phen)Cl_3·2H_2O. Its fluorescence spectra were studied. The results show that the strong fluorescence emitting of 592...The complex of Eu 3+ and Enoxacin(ENX) and Phen was synthesized. Its compositions is Eu(ENX)_3(phen)Cl_3·2H_2O. Its fluorescence spectra were studied. The results show that the strong fluorescence emitting of 592 and 616 nm for Eu 3+ in the Eu(ENX)_3(phen)Cl_3·2H_2O complex is related to the transitions 5D_0-7F_1 and 5D_0-7F_2 respectively. A sensitive method for the determination of adenosine triphosphate(ATP) by fluorescence quenching is proposed. The method is based on the ability of ATP to inhibit the formation of a strong fluorescent complex of Eu(ENX)_3(phen)Cl_3·2H_2O. In conditions of pH 6.7 in HAc-NaAc buffer and λ_ ex=340 nm and λ_ em=616 nm, the linear range of the determination is 0.4～ 10 μg·ml -1 and the detection limit is 0.034 μg·ml -1 for ATP. The method was applied to determine ATP in adenosine disodium triphosphate injection samples with relative standard deviation of 212% and recovery of 94.8%～1037%.展开更多
A new complex Tb(IB)_3(phen)·2H_2O that gives off green fluorescence was synthesized. The results show that the strong fluorescence emitting of 490 and 545 nm for Tb 3+ in the Tb(IB)_3(phen)·2H_2O complex is...A new complex Tb(IB)_3(phen)·2H_2O that gives off green fluorescence was synthesized. The results show that the strong fluorescence emitting of 490 and 545 nm for Tb 3+ in the Tb(IB)_3(phen)·2H_2O complex is related to the transitions 5D_4-7F_6 and 5D_4-7F_5, respectively. The results indicate that the complex is concentrated on the nuclei regions in the section of onion toot tip tissues and the nuclei are high lighted under fluorescent microscope. It is possible that the Tb(IB)_3(phen)·2H_2O complex can be developed as a fluorescent dye in biological and pathological studies.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
A novel β-diketone, 1-（3,4,5-trisbenzyloxy）benzoyl-5-benzoyl acetylacetone （TBAA）, and its corresponding binary Tb（Ⅲ） complex Tb（TBAA）3·2H2O and ternary complex Tb（TBAA）3Phen with 1,10-phenanthroline ...A novel β-diketone, 1-（3,4,5-trisbenzyloxy）benzoyl-5-benzoyl acetylacetone （TBAA）, and its corresponding binary Tb（Ⅲ） complex Tb（TBAA）3·2H2O and ternary complex Tb（TBAA）3Phen with 1,10-phenanthroline （Phen） were prepared. The ligand was characterized based on elemental analysis, FT-IR, and 1H NMR. The complexes were characterized with elemental analysis, FT-IR and thermogravimetry and derivative thermogravimetry （TG-DTG）. Photoluminescence measurements indicated that the energy absorbed by the organic ligand was efficiently transferred to the central Tb3＋ ions, and the complex showed intense and characteristic emissions due to the 5D4→7FJ transitions of the central Tb3＋ ions. Both complexes showed longer fluorescence lifetimes. After the introduction of the second ligand Phen group, the relative emission intensities and fluorescence lifetimes of the ternary complex Tb（TBAA）3Phen enhanced more obviously than that of the binary complex Tb（TBAA）3·2H2O. This indicated that the presence of the ligand TBAA and the second ligand Phen could sensitize fluorescence intensities of Tb（Ⅲ） ions, and the introduction of Phen group resulted in the enhancement of the fluorescence properties of the Tb（Ⅲ） ternary rare earth complex.展开更多
The structure of addition compound Cu(phen)3(PMoxdH)(CO4)2 was establish ed by means of X-ray crystallography,where PMoxdH is N,N-Bi(2-pyridyl-methyl)-oxamide,in which six nitrogen atoms of the three 1,10,-phen-anthro...The structure of addition compound Cu(phen)3(PMoxdH)(CO4)2 was establish ed by means of X-ray crystallography,where PMoxdH is N,N-Bi(2-pyridyl-methyl)-oxamide,in which six nitrogen atoms of the three 1,10,-phen-anthroline bind to the copper ion and the oxygen atom of PMoxdH is uncoordinated.展开更多
A new mononuclear Cu（Ⅱ） dithiocarbamate complex CuI（prdtc）（phen） 1 （prdtc = N-pyrrolidinyldithiocarbamate, phen = 1,10-phenanthroline） was synthesized and characterized by elemental analysis, IR spectrum, and...A new mononuclear Cu（Ⅱ） dithiocarbamate complex CuI（prdtc）（phen） 1 （prdtc = N-pyrrolidinyldithiocarbamate, phen = 1,10-phenanthroline） was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 8.7110（9）, b = 14.7143（14）, c = 14.8507（15） A, β = 109.721（6）°, V = 1791.9（3） A3, Z = 4, Dc = 1.916 g/cm3, CI7H16CulN3S2, Mr = 516.89, λ（MoKa） = 0.71073A,μ = 3.178 mm^-1, F（000） = 1012, the final R = 0.0369 and wR = 0.0987. A total of 4082 unique reflections were collected, of which 2916 with I 〉 2σ（I） were observed. The Cu（Ⅱ） atom is five-coordinated in a distorted square-pyramidal geometry by one I atom in the apical position, two S atoms from a prdtc ligand and two N atoms from a phen ligand in the basal plane. There exist face-to-face aromatic π-π stacking interactions between adjacent phen ligands stabilizing the structure and making the complex assemble into a 1D structure along the a axis. It can be concluded that the difference of the dtc flexibility and reaction conditions result in the structural difference between complex 1 and CuI（dmdtc）（phen） （dmdtc = N, N-dimethyldithiocarbamate）.展开更多
A new compound（ClO4）2（H2O）0.5（azpy）was synthesized.Its structure was determined by single X-ray diffraction.The crystal belongs to triclinic system,space group P1.The crystallographic data:a=11.813（2）,b=12.574...A new compound（ClO4）2（H2O）0.5（azpy）was synthesized.Its structure was determined by single X-ray diffraction.The crystal belongs to triclinic system,space group P1.The crystallographic data:a=11.813（2）,b=12.574（2）,c=14.580（3）*!,a=84.048（6）,β=77.878（15）,γ=67.902（12）°,V=1961.1（7）*!3,Z=2,F（000）=926,Mr=904.57,Dc=1.532Mg/m3,μ=0.542mm-1,R1=0.0770,and wR2=0.1373.In the ctystal Mn（Ⅱ）ion is coordinated with six nitrogen from three phen ligands to form a distorted octahedron geometry.展开更多
The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated b...The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ>3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.展开更多
文摘Time-resolved fluorescence spectra of europium methylbenzoates (MBA)with 1,10-phenanthroline(phen)have been measured at room temperature.For each of the europium chelates,where the ligand triple states lie above the ~5D_1 level of Eu^(3-),the spectra providc evidence that the Eu^(3-) ~5D_0 state is populated by nonradiative energy transfer from the higher-lying ~5D_1,state.The relaxation time for energy decay from ~5D_1 state is measured in the microcrystals to bc of the order of a few microseconds.It is suggested that the ligand C=0 and C=C stretching vibrations and Eu-O vibrations,chclate ring and benzene ring vibrations make important contributions to the relaxation process.The ~5D\-1—~5D\-0 relaxation time of Eu- (p-MBA)_3phen is shorter than those of Eu(m-MBA)_3phen and Eu(o-MBA)_3phen since nonradiative degradation to ~5D_0 from ~5D_1 appears to be more strongly influenced by the E_u^(3+)sites in the former.
文摘The complex Eu(IB)_3(phen)·2H_2O was synthesized. The results show that the strong fluorescence emitting of 593 and 615 nm for Eu^(3+) in the Eu(IB)_3(phen) complex is related to the transitions (()~5D_0-()~7F_1) and (()~5D_0-()~7F_2,) respectively. A sensitive method for the determination of adenosine disodium triphosphate (ATP) by fluorescence quenching is proposed. The method is based on the ability of ATP to inhibit the formation of a strong fluorescent complex of Eu(IB)_3(phen). In conditions of pH 6.7 HAc-NaAc buffer, λ_(ex)=273 nm and λ_(em)=615 nm, the linear range of the determination was 0.1～10 μg·ml^(-1) and the detection limit was 0.03 μg·ml^(-1) for ATP. The method has been applied to determine ATP in adenosine disodium triphosphate tablets samples with relative standard deviation of 2.18% and recovery of (98.4%～)104.0%.
文摘The complex of Eu 3+ and Enoxacin(ENX) and Phen was synthesized. Its compositions is Eu(ENX)_3(phen)Cl_3·2H_2O. Its fluorescence spectra were studied. The results show that the strong fluorescence emitting of 592 and 616 nm for Eu 3+ in the Eu(ENX)_3(phen)Cl_3·2H_2O complex is related to the transitions 5D_0-7F_1 and 5D_0-7F_2 respectively. A sensitive method for the determination of adenosine triphosphate(ATP) by fluorescence quenching is proposed. The method is based on the ability of ATP to inhibit the formation of a strong fluorescent complex of Eu(ENX)_3(phen)Cl_3·2H_2O. In conditions of pH 6.7 in HAc-NaAc buffer and λ_ ex=340 nm and λ_ em=616 nm, the linear range of the determination is 0.4～ 10 μg·ml -1 and the detection limit is 0.034 μg·ml -1 for ATP. The method was applied to determine ATP in adenosine disodium triphosphate injection samples with relative standard deviation of 212% and recovery of 94.8%～1037%.
文摘A new complex Tb(IB)_3(phen)·2H_2O that gives off green fluorescence was synthesized. The results show that the strong fluorescence emitting of 490 and 545 nm for Tb 3+ in the Tb(IB)_3(phen)·2H_2O complex is related to the transitions 5D_4-7F_6 and 5D_4-7F_5, respectively. The results indicate that the complex is concentrated on the nuclei regions in the section of onion toot tip tissues and the nuclei are high lighted under fluorescent microscope. It is possible that the Tb(IB)_3(phen)·2H_2O complex can be developed as a fluorescent dye in biological and pathological studies.
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Project supported by Shanxi (20072194 and 20072185) Provincial Youth Technology Research Foundationthe Foundation of Taiyuan Graduate Innovation (100115133 and 100115131)
文摘A novel β-diketone, 1-（3,4,5-trisbenzyloxy）benzoyl-5-benzoyl acetylacetone （TBAA）, and its corresponding binary Tb（Ⅲ） complex Tb（TBAA）3·2H2O and ternary complex Tb（TBAA）3Phen with 1,10-phenanthroline （Phen） were prepared. The ligand was characterized based on elemental analysis, FT-IR, and 1H NMR. The complexes were characterized with elemental analysis, FT-IR and thermogravimetry and derivative thermogravimetry （TG-DTG）. Photoluminescence measurements indicated that the energy absorbed by the organic ligand was efficiently transferred to the central Tb3＋ ions, and the complex showed intense and characteristic emissions due to the 5D4→7FJ transitions of the central Tb3＋ ions. Both complexes showed longer fluorescence lifetimes. After the introduction of the second ligand Phen group, the relative emission intensities and fluorescence lifetimes of the ternary complex Tb（TBAA）3Phen enhanced more obviously than that of the binary complex Tb（TBAA）3·2H2O. This indicated that the presence of the ligand TBAA and the second ligand Phen could sensitize fluorescence intensities of Tb（Ⅲ） ions, and the introduction of Phen group resulted in the enhancement of the fluorescence properties of the Tb（Ⅲ） ternary rare earth complex.
文摘The structure of addition compound Cu(phen)3(PMoxdH)(CO4)2 was establish ed by means of X-ray crystallography,where PMoxdH is N,N-Bi(2-pyridyl-methyl)-oxamide,in which six nitrogen atoms of the three 1,10,-phen-anthroline bind to the copper ion and the oxygen atom of PMoxdH is uncoordinated.
基金supported by the National Natural Science Foundation of China (Nos. 50572030 and 50372022)the Research Fund of Huaqiao University (No. 06BS216)the Young Talent Program of Fujian Province (No. 2007F3060)
文摘A new mononuclear Cu（Ⅱ） dithiocarbamate complex CuI（prdtc）（phen） 1 （prdtc = N-pyrrolidinyldithiocarbamate, phen = 1,10-phenanthroline） was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 8.7110（9）, b = 14.7143（14）, c = 14.8507（15） A, β = 109.721（6）°, V = 1791.9（3） A3, Z = 4, Dc = 1.916 g/cm3, CI7H16CulN3S2, Mr = 516.89, λ（MoKa） = 0.71073A,μ = 3.178 mm^-1, F（000） = 1012, the final R = 0.0369 and wR = 0.0987. A total of 4082 unique reflections were collected, of which 2916 with I 〉 2σ（I） were observed. The Cu（Ⅱ） atom is five-coordinated in a distorted square-pyramidal geometry by one I atom in the apical position, two S atoms from a prdtc ligand and two N atoms from a phen ligand in the basal plane. There exist face-to-face aromatic π-π stacking interactions between adjacent phen ligands stabilizing the structure and making the complex assemble into a 1D structure along the a axis. It can be concluded that the difference of the dtc flexibility and reaction conditions result in the structural difference between complex 1 and CuI（dmdtc）（phen） （dmdtc = N, N-dimethyldithiocarbamate）.
文摘A new compound（ClO4）2（H2O）0.5（azpy）was synthesized.Its structure was determined by single X-ray diffraction.The crystal belongs to triclinic system,space group P1.The crystallographic data:a=11.813（2）,b=12.574（2）,c=14.580（3）*!,a=84.048（6）,β=77.878（15）,γ=67.902（12）°,V=1961.1（7）*!3,Z=2,F（000）=926,Mr=904.57,Dc=1.532Mg/m3,μ=0.542mm-1,R1=0.0770,and wR2=0.1373.In the ctystal Mn（Ⅱ）ion is coordinated with six nitrogen from three phen ligands to form a distorted octahedron geometry.
文摘The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ>3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.
