A new organic-inorganic hybrid sandwich-type polyoxotungstate [Cu（dien）-（H2O）2]2[{Cu（dien）（H2O）}3{Cu（4.5）W（0.5）（B-α-Sb W9O（33））2}]（OH）4·7H2O（1, dien = diethylenetriamine） has been hydrotherma...A new organic-inorganic hybrid sandwich-type polyoxotungstate [Cu（dien）-（H2O）2]2[{Cu（dien）（H2O）}3{Cu（4.5）W（0.5）（B-α-Sb W9O（33））2}]（OH）4·7H2O（1, dien = diethylenetriamine） has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, TG analysis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, C2/c, a = 31.527（3）, b = 13.9309（13）, c = 24.297（2） A, β = 1108.269（2）°, V = 10133.2（17） A3, Dc = 4.024 g/cm3 and Z = 4. X-ray crystallographic study shows that the molecular structure of 1contains an infrequent penta-nuclearity {Cu4.5W0.5} cluster sandwiched polyanion [{Cu4.5W0.5（B-α-Sb W9O33）2}]6-, on which three [Cu（dien）（H2O）]2＋ complexes decorated as pendants. Interestingly, two [Cu（dien）（H2O）]2＋ pendants linked the two neighboring sandwich-type polyanions via double Cu-μ2-O-W bridges, resulting in a 1-D chain. The magnetic measurements show compound 1exhibits obvious antiferromagnetic interactions.展开更多
A series of inorganic-organic hybrids K2NamH9-m[{Ln(GeW11O39)2}{Cu2(bpy)2(μ-ox)}]·nH2O(bpy=2,2-bipyridine and ox= oxalate;Ln=La,Nd,Sm,Eu,Gd;n=19,17,22,20,19;m=4,4,4,9,2)were isolated after reacting in a potassiu...A series of inorganic-organic hybrids K2NamH9-m[{Ln(GeW11O39)2}{Cu2(bpy)2(μ-ox)}]·nH2O(bpy=2,2-bipyridine and ox= oxalate;Ln=La,Nd,Sm,Eu,Gd;n=19,17,22,20,19;m=4,4,4,9,2)were isolated after reacting in a potassium acetate buffer.X-ray structural analyses show that compounds 1-5 are isomorphic and consist of[Ln(GeW11O39)2] 13-polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure.The 1D chain further connects into the 3D framework byπ-πinteractions with neighboring bpy groups.The magnetic susceptibility data indicate that anti-ferromagnetic coupling between the neighboring Cu2+ions in the structure and the rare earth ions affects magnetic property of the structure.展开更多
The magnetic exchange interactions between the dimanganese(II)-substituted complexes and the het-eropolymolyanion, [MnII2(Xn+Mo9O33)2]2(n-10)-(X = PV(I), AsV(II) and SeVI(III)), are investigated by using density funct...The magnetic exchange interactions between the dimanganese(II)-substituted complexes and the het-eropolymolyanion, [MnII2(Xn+Mo9O33)2]2(n-10)-(X = PV(I), AsV(II) and SeVI(III)), are investigated by using density functional theory combined with broken-symmetry approach (DFT-BS) method. The calculated magnetic exchange coupling constant (J) of complex II is in reasonable agreement with the responding experimental value and the negative J values indicate that antiferromagnetic exchange interactions exist in these complexes. Furthermore, the influence of the central heteroatom on the exchange cou-pling within the dimanganese core unit is studied from standpoints of geometry, spin density and fron-tier orbitals. It demonstrates that the change of the heteroatom X via PV-AsV-SeVI elongates the dis-tances of Mn1···Mn2 and shortens the distances of Ob···Ob, and reduces the effectiveness of the super-exchange pathways, consequently, decreasing the magnitude of the antiferromagnetic coupling constant, J, of these species.展开更多
基金supported by the Foundation of Education Department of Henan Province(15A150037)
文摘A new organic-inorganic hybrid sandwich-type polyoxotungstate [Cu（dien）-（H2O）2]2[{Cu（dien）（H2O）}3{Cu（4.5）W（0.5）（B-α-Sb W9O（33））2}]（OH）4·7H2O（1, dien = diethylenetriamine） has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, TG analysis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, C2/c, a = 31.527（3）, b = 13.9309（13）, c = 24.297（2） A, β = 1108.269（2）°, V = 10133.2（17） A3, Dc = 4.024 g/cm3 and Z = 4. X-ray crystallographic study shows that the molecular structure of 1contains an infrequent penta-nuclearity {Cu4.5W0.5} cluster sandwiched polyanion [{Cu4.5W0.5（B-α-Sb W9O33）2}]6-, on which three [Cu（dien）（H2O）]2＋ complexes decorated as pendants. Interestingly, two [Cu（dien）（H2O）]2＋ pendants linked the two neighboring sandwich-type polyanions via double Cu-μ2-O-W bridges, resulting in a 1-D chain. The magnetic measurements show compound 1exhibits obvious antiferromagnetic interactions.
文摘A series of inorganic-organic hybrids K2NamH9-m[{Ln(GeW11O39)2}{Cu2(bpy)2(μ-ox)}]·nH2O(bpy=2,2-bipyridine and ox= oxalate;Ln=La,Nd,Sm,Eu,Gd;n=19,17,22,20,19;m=4,4,4,9,2)were isolated after reacting in a potassium acetate buffer.X-ray structural analyses show that compounds 1-5 are isomorphic and consist of[Ln(GeW11O39)2] 13-polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure.The 1D chain further connects into the 3D framework byπ-πinteractions with neighboring bpy groups.The magnetic susceptibility data indicate that anti-ferromagnetic coupling between the neighboring Cu2+ions in the structure and the rare earth ions affects magnetic property of the structure.
基金Supported by the National Natural Science Foundation of China (Grant No. 20703008)Program for Changjiang Scholars and Innovative Research Team in University (Grant No. IRT0714)
文摘The magnetic exchange interactions between the dimanganese(II)-substituted complexes and the het-eropolymolyanion, [MnII2(Xn+Mo9O33)2]2(n-10)-(X = PV(I), AsV(II) and SeVI(III)), are investigated by using density functional theory combined with broken-symmetry approach (DFT-BS) method. The calculated magnetic exchange coupling constant (J) of complex II is in reasonable agreement with the responding experimental value and the negative J values indicate that antiferromagnetic exchange interactions exist in these complexes. Furthermore, the influence of the central heteroatom on the exchange cou-pling within the dimanganese core unit is studied from standpoints of geometry, spin density and fron-tier orbitals. It demonstrates that the change of the heteroatom X via PV-AsV-SeVI elongates the dis-tances of Mn1···Mn2 and shortens the distances of Ob···Ob, and reduces the effectiveness of the super-exchange pathways, consequently, decreasing the magnitude of the antiferromagnetic coupling constant, J, of these species.
