24-Membered macrocyclic bicopper(Ⅱ) complexes wth bridging ligand imidzao-late,SCN-,N3-and H2O respectively were synthesized by condensation of diacetylpyridine with 3-oxapentane-1,5-diamine.As the model compounds o... 24-Membered macrocyclic bicopper(Ⅱ) complexes wth bridging ligand imidzao-late,SCN-,N3-and H2O respectively were synthesized by condensation of diacetylpyridine with 3-oxapentane-1,5-diamine.As the model compounds of superoxide dismutase (SOD),the relationship between their SOD activities and properties of bridging ligands and redox potentials of copper(Ⅱ) were studied.展开更多
<正> Three novel 16-member macrocyclic complexes containing 4 manganese atoms on ring and 2phthalate as bridging ligand have been synthesized.The composition of the complexes has been determinedby elemental anal...<正> Three novel 16-member macrocyclic complexes containing 4 manganese atoms on ring and 2phthalate as bridging ligand have been synthesized.The composition of the complexes has been determinedby elemental analyses and characterized by IR and magnetic balance.The crystal structure of the complex[Mn4（μ-phth）2（bpy）8]（ClO4）·3H2O has been determined.Crystal data:space group P （?）,with a=14.276（6）,b=14.369（9）,c=15.540（1） （?）,α=70.22（5）,β=61.73（6）,γ=66.38（5）°,Z=1.The vari-able-temperature magnetic susceptibility （4-300 K） of [Mn4（μ-phth）2（bpy）8] （ClO4）4·3H2O and [Mn4（μ-phth）2（phen）8]（ClO4）)4·2H2O has been determined and the susceptibility data are least squares fit tothe susceptibility equation derived from the spin Hamihonian （?）=-2J（（?）1·（?）2+（?）2·（?）3+（?）3·（?）4+（?）1·（?）4）.The exchange intergral,J,has been found equal to 0.53 cm-1（bpy） and 0.23 cm-1（phen）.This indi-cates a weak ferromagnetic spin exchange interaction among the metal ions.展开更多
Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure usi...Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure using rare earth metal isothiocyanates. These complexesare characterized by elemental analyses, FABMS, IR, conductivity and magnetic susceptibility.The variable-temperature magnetic susceptibility (4--300K) of complexes of Gd(Ⅲ) and Tb(Ⅲ) has been determined. A satisfactory fit to theoretical curve derived from spin Hamil-tonian operator was obtained by least squares method. The exchange interaction parameters areJ =-0.220 cm^(-1) for Gd, ,ZJ~?=-0.052 cm^(-1) for Tb. The results indicate a very weak anti-ferromagnetic interaction between Gd^(3+)-Gd^(3+), Tb^(3+)-Tb^(3+) ions.展开更多
Nine homobinuclear lanthanide complexes with macrocyclic Schiff base were prepared by condensing 2, 6-diacetylpyridine and 1, 3-diamino-2-hydroxypropane in the presence of template lanthanide metal ions. These complex...Nine homobinuclear lanthanide complexes with macrocyclic Schiff base were prepared by condensing 2, 6-diacetylpyridine and 1, 3-diamino-2-hydroxypropane in the presence of template lanthanide metal ions. These complexes were characterized by elemental analysis, IR, molar conductance and magnetic susceptibility. The variable-temperature magnetic susceptibility (4-300 K) of complexes of Gd( Ⅲ ) and Dy( Ⅲ ) was determined. A satisfactory fit to theoretical curve derived from spin Hamiltonian operator was obtained using least-squares method. The exchange interaction parameters are J=-0.26 cm-1, g=1.98 and △=0.06 cm-1, Z.J'=-0. 21 cm-1,g'=1.33 for Gd( Ⅲ ) and Dy( Ⅲ ), respectively. The results indicate a very week antiferromagnetic interaction between Gd( Ⅲ )-Gd( Ⅲ ) and Dy( Ⅲ )-Dy( Ⅲ ) ions.展开更多
The crystal structure of the title complex, [NiL], has been determined by using X-ray analysis (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(methoxycarbonyl)-1,4,8,11-tetraazacyclotetra- deca-7,11-diene). Crystal data: ...The crystal structure of the title complex, [NiL], has been determined by using X-ray analysis (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(methoxycarbonyl)-1,4,8,11-tetraazacyclotetra- deca-7,11-diene). Crystal data: C22H18N4O6Ni, Mr = 493.11, triclinic, space group P, a = 9.128(6), b = 9.941(7), c = 12.396(8) ? a = 107.11(1), b = 106.14(1), g = 97.69(1), V = 1003.9(11) 3, Z = 2, Dc = 1.631 g/cm3, m(MoKa) = 1.018 mm-1, F(000) = 508, R = 0.0584 and wR = 0.0981 for 1724 observed reflections with I > 2s(I). The Ni(II) atom is coordinated by four nitrogen donors of the macrocyclic ligand with a slightly distorted square-planar geometry. In the crystal, the CH…O hydrogen bonds link the complex molecules to form infinite 1D chains which are further linked by p…p stacking interactions to form chain-pairs.展开更多
Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-r...Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-ray single-crystal diffraction analysis. Complex 1 belongs to the trigonal system, space group R-3 with a = b = 19.2730（5）, c = 23.6890（13）A^°, V= 7620.4（5） A^°^3, Z = 6, Dc= 1.553 g/cm^3,μ= 1.518 mm^-1, F（000） = 3600, R = 0.0238 and wR = 0.0636. Complex 2 is of monoelinie system, space group P21/c with a = 13.7550（8）, b = 11.5425（7）, c = 12.7876（7）A^°, β= 93.585（1）°, V = 2026.3（2） A^°^3, Z = 4, Dc= 1.548 g/cm^3,μ = 1.286 mm^-1, F（000） = 976, R = 0.0298 and wR = 0.0722. Complex 1 is a cyclic trimer with a macrocyclic 12-membered ring structure formed by the bidentate bridging coordination of carboxylate group to tin atoms. The tin atom is six-coordinated in a distorted octahedral geometry. In complex 2, the distorted trigonal bipyramidal Et2SnL2 units are linked into polymeric chains by the weak Sn…O interaction involving Sn and the earbonyl O of an adjacent ligand, and the chains are further connected by intermolecular N-H…O hydrogen bonds to form a two-dimensional supramolecular structure.展开更多
Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic a...Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.展开更多
The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: ...The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.展开更多
基金Project supported by the National Natural Science Foundation of China.
文摘 24-Membered macrocyclic bicopper(Ⅱ) complexes wth bridging ligand imidzao-late,SCN-,N3-and H2O respectively were synthesized by condensation of diacetylpyridine with 3-oxapentane-1,5-diamine.As the model compounds of superoxide dismutase (SOD),the relationship between their SOD activities and properties of bridging ligands and redox potentials of copper(Ⅱ) were studied.
基金the National Natural Science Foundation of China.
文摘<正> Three novel 16-member macrocyclic complexes containing 4 manganese atoms on ring and 2phthalate as bridging ligand have been synthesized.The composition of the complexes has been determinedby elemental analyses and characterized by IR and magnetic balance.The crystal structure of the complex[Mn4（μ-phth）2（bpy）8]（ClO4）·3H2O has been determined.Crystal data:space group P （?）,with a=14.276（6）,b=14.369（9）,c=15.540（1） （?）,α=70.22（5）,β=61.73（6）,γ=66.38（5）°,Z=1.The vari-able-temperature magnetic susceptibility （4-300 K） of [Mn4（μ-phth）2（bpy）8] （ClO4）4·3H2O and [Mn4（μ-phth）2（phen）8]（ClO4）)4·2H2O has been determined and the susceptibility data are least squares fit tothe susceptibility equation derived from the spin Hamihonian （?）=-2J（（?）1·（?）2+（?）2·（?）3+（?）3·（?）4+（?）1·（?）4）.The exchange intergral,J,has been found equal to 0.53 cm-1（bpy） and 0.23 cm-1（phen）.This indi-cates a weak ferromagnetic spin exchange interaction among the metal ions.
基金Project supported by the National Natural Science Foundation of China.
文摘Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure using rare earth metal isothiocyanates. These complexesare characterized by elemental analyses, FABMS, IR, conductivity and magnetic susceptibility.The variable-temperature magnetic susceptibility (4--300K) of complexes of Gd(Ⅲ) and Tb(Ⅲ) has been determined. A satisfactory fit to theoretical curve derived from spin Hamil-tonian operator was obtained by least squares method. The exchange interaction parameters areJ =-0.220 cm^(-1) for Gd, ,ZJ~?=-0.052 cm^(-1) for Tb. The results indicate a very weak anti-ferromagnetic interaction between Gd^(3+)-Gd^(3+), Tb^(3+)-Tb^(3+) ions.
基金Supported by the National Natural Science Foundation of China
文摘Nine homobinuclear lanthanide complexes with macrocyclic Schiff base were prepared by condensing 2, 6-diacetylpyridine and 1, 3-diamino-2-hydroxypropane in the presence of template lanthanide metal ions. These complexes were characterized by elemental analysis, IR, molar conductance and magnetic susceptibility. The variable-temperature magnetic susceptibility (4-300 K) of complexes of Gd( Ⅲ ) and Dy( Ⅲ ) was determined. A satisfactory fit to theoretical curve derived from spin Hamiltonian operator was obtained using least-squares method. The exchange interaction parameters are J=-0.26 cm-1, g=1.98 and △=0.06 cm-1, Z.J'=-0. 21 cm-1,g'=1.33 for Gd( Ⅲ ) and Dy( Ⅲ ), respectively. The results indicate a very week antiferromagnetic interaction between Gd( Ⅲ )-Gd( Ⅲ ) and Dy( Ⅲ )-Dy( Ⅲ ) ions.
基金This work was supported by the National Natural Science Foundation of China (20071019, 50172021 and 90101028)
文摘The crystal structure of the title complex, [NiL], has been determined by using X-ray analysis (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(methoxycarbonyl)-1,4,8,11-tetraazacyclotetra- deca-7,11-diene). Crystal data: C22H18N4O6Ni, Mr = 493.11, triclinic, space group P, a = 9.128(6), b = 9.941(7), c = 12.396(8) ? a = 107.11(1), b = 106.14(1), g = 97.69(1), V = 1003.9(11) 3, Z = 2, Dc = 1.631 g/cm3, m(MoKa) = 1.018 mm-1, F(000) = 508, R = 0.0584 and wR = 0.0981 for 1724 observed reflections with I > 2s(I). The Ni(II) atom is coordinated by four nitrogen donors of the macrocyclic ligand with a slightly distorted square-planar geometry. In the crystal, the CH…O hydrogen bonds link the complex molecules to form infinite 1D chains which are further linked by p…p stacking interactions to form chain-pairs.
基金supported by the NNSFC (20701027)the Post-Doctor Innovation Project of Shandong Province (200702021) the Key Laboratory of Colloid Interface Chemistry of Ministry of Education (200707)
文摘Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-ray single-crystal diffraction analysis. Complex 1 belongs to the trigonal system, space group R-3 with a = b = 19.2730（5）, c = 23.6890（13）A^°, V= 7620.4（5） A^°^3, Z = 6, Dc= 1.553 g/cm^3,μ= 1.518 mm^-1, F（000） = 3600, R = 0.0238 and wR = 0.0636. Complex 2 is of monoelinie system, space group P21/c with a = 13.7550（8）, b = 11.5425（7）, c = 12.7876（7）A^°, β= 93.585（1）°, V = 2026.3（2） A^°^3, Z = 4, Dc= 1.548 g/cm^3,μ = 1.286 mm^-1, F（000） = 976, R = 0.0298 and wR = 0.0722. Complex 1 is a cyclic trimer with a macrocyclic 12-membered ring structure formed by the bidentate bridging coordination of carboxylate group to tin atoms. The tin atom is six-coordinated in a distorted octahedral geometry. In complex 2, the distorted trigonal bipyramidal Et2SnL2 units are linked into polymeric chains by the weak Sn…O interaction involving Sn and the earbonyl O of an adjacent ligand, and the chains are further connected by intermolecular N-H…O hydrogen bonds to form a two-dimensional supramolecular structure.
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 2 7)
文摘Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.
基金The project was supported by the funds of the Key Laboratory of Organic Syntheses of Jiangsu province(KJS01018) and Funds of Young Teacher of Suzhou University
文摘The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.
