Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni2(Bpy)3(Dto)2(H2O)3 (1), Ni2(Phen)3(Dto)2(H2O)3 (2) and Ni2(Me2Bpy)3(Dto)2(H2O)2 (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline...Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni2(Bpy)3(Dto)2(H2O)3 (1), Ni2(Phen)3(Dto)2(H2O)3 (2) and Ni2(Me2Bpy)3(Dto)2(H2O)2 (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline, Me2Bpy=4,4′-dimethyl-2,2′-bipyridine, Dto2-=Dithiooxalate), and characterized by elemental analyses, IR, UV-Visible spectra, conductance. The variable temperature magnetic susceptibilities for the complexes were measured in the range of temperature between 1.5 K and 298 K. Experimental data of magnetic susceptibility were successfully fit to theoretical value based on the spin Hamiltonian operator: H=-2JS1S2, S1=S2=1, giving the magnetic exchange parameters of 2J=-52.8 cm-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions. The magnetic exchange parameters of the binuclear Nickel(Ⅱ) complexes bridged with dithiooxalate is larger than that of the binuclear Nickel(Ⅱ) complexes bridged with oxalate. Dithiooxalate is more effective to transfer antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions than oxalate.展开更多
Treatment of a heptadentate ligand 2,2＇-（（（pyridine-2,6-diyl-bis（methylene））- bis（（pyridin-2-ylmethyl）azanediyl））bis（methylene））diphenol （H2L） possessing pyridinyl- and phenolate groups, with three eq...Treatment of a heptadentate ligand 2,2＇-（（（pyridine-2,6-diyl-bis（methylene））- bis（（pyridin-2-ylmethyl）azanediyl））bis（methylene））diphenol （H2L） possessing pyridinyl- and phenolate groups, with three equivalents of Cu（C104）2·6H2O in methanol under base conditions, gave rise to a hexanuclear cluster complex [Cu6L2（OH）4]（C104）4·4MeCN·0.5MeOH （1）. Complex 1 crystallizes in triclinic, space group Pi with a = 12.068（12）, b = 12.567（12）, c = 16.279（16） A, α = 105.694（12）, β = 93.631（13）, γ = 112.017（11）°, V= 2166（4） A3, Z = 1,μ= 1.651 mm^-1, Dc = 1.599 Mg/m^3, T = 296（2） K, C74.5H795N14O24.5Cl4Cu6, Mr = 2086.12, F（000） = 1062.5, S = 1.061, R = 0.0521 and wR = 0.1270. In the cation of complex 1, the six copper cores are arranged into a two-parallel three-site strings configuration with each metal exhibits a slightly distorted square-pyramidal geometry, resulting from the connection of donor pyridinyi nitrogen and phenolate oxygen atoms in ligand H2L, and/or the oxygen donors in hydroxyl groups. In addition, magnetic susceptibility measurements revealed complex 1 displayed antiferromagnetic coupling.展开更多
The complexation oflanthanide(Ⅲ) cations with 1,2-propanediaminetetraacetate (1,2-PDTA) in aqueous solution has been investigated by ^(23)Na,^(35)Cl,~2H and ^(17)O NMR shift measurements.It has been shown that the co...The complexation oflanthanide(Ⅲ) cations with 1,2-propanediaminetetraacetate (1,2-PDTA) in aqueous solution has been investigated by ^(23)Na,^(35)Cl,~2H and ^(17)O NMR shift measurements.It has been shown that the contact shifts are dominant for ^(17)O,^(35)Cl and ~2H (only for the heavier lanthanide series) and the pseudocontact shifts are dominant for ^(23)Na.It is suggested that the 1,2-PDTA ligand is bound pentadentately via the two nitrogens and the three carboxylates for the lighter lanthanide complexes,hexdentately via the two nitrogens and the four carboxylates for the heavier ones.The numbers of the water coordinated were determined.The small amount of chloride anion in inner coordination sphere was observed.展开更多
文摘Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni2(Bpy)3(Dto)2(H2O)3 (1), Ni2(Phen)3(Dto)2(H2O)3 (2) and Ni2(Me2Bpy)3(Dto)2(H2O)2 (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline, Me2Bpy=4,4′-dimethyl-2,2′-bipyridine, Dto2-=Dithiooxalate), and characterized by elemental analyses, IR, UV-Visible spectra, conductance. The variable temperature magnetic susceptibilities for the complexes were measured in the range of temperature between 1.5 K and 298 K. Experimental data of magnetic susceptibility were successfully fit to theoretical value based on the spin Hamiltonian operator: H=-2JS1S2, S1=S2=1, giving the magnetic exchange parameters of 2J=-52.8 cm-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions. The magnetic exchange parameters of the binuclear Nickel(Ⅱ) complexes bridged with dithiooxalate is larger than that of the binuclear Nickel(Ⅱ) complexes bridged with oxalate. Dithiooxalate is more effective to transfer antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions than oxalate.
基金Financially supported by the Education Department of Jiangxi Province(No.JXJG-14-10-6)Jiangxi Science and Technology Normal University
文摘Treatment of a heptadentate ligand 2,2＇-（（（pyridine-2,6-diyl-bis（methylene））- bis（（pyridin-2-ylmethyl）azanediyl））bis（methylene））diphenol （H2L） possessing pyridinyl- and phenolate groups, with three equivalents of Cu（C104）2·6H2O in methanol under base conditions, gave rise to a hexanuclear cluster complex [Cu6L2（OH）4]（C104）4·4MeCN·0.5MeOH （1）. Complex 1 crystallizes in triclinic, space group Pi with a = 12.068（12）, b = 12.567（12）, c = 16.279（16） A, α = 105.694（12）, β = 93.631（13）, γ = 112.017（11）°, V= 2166（4） A3, Z = 1,μ= 1.651 mm^-1, Dc = 1.599 Mg/m^3, T = 296（2） K, C74.5H795N14O24.5Cl4Cu6, Mr = 2086.12, F（000） = 1062.5, S = 1.061, R = 0.0521 and wR = 0.1270. In the cation of complex 1, the six copper cores are arranged into a two-parallel three-site strings configuration with each metal exhibits a slightly distorted square-pyramidal geometry, resulting from the connection of donor pyridinyi nitrogen and phenolate oxygen atoms in ligand H2L, and/or the oxygen donors in hydroxyl groups. In addition, magnetic susceptibility measurements revealed complex 1 displayed antiferromagnetic coupling.
基金Project supported by the National Natural Science Foundation of China
文摘The complexation oflanthanide(Ⅲ) cations with 1,2-propanediaminetetraacetate (1,2-PDTA) in aqueous solution has been investigated by ^(23)Na,^(35)Cl,~2H and ^(17)O NMR shift measurements.It has been shown that the contact shifts are dominant for ^(17)O,^(35)Cl and ~2H (only for the heavier lanthanide series) and the pseudocontact shifts are dominant for ^(23)Na.It is suggested that the 1,2-PDTA ligand is bound pentadentately via the two nitrogens and the three carboxylates for the lighter lanthanide complexes,hexdentately via the two nitrogens and the four carboxylates for the heavier ones.The numbers of the water coordinated were determined.The small amount of chloride anion in inner coordination sphere was observed.
