A new 3d-4f（CuⅡ-CeⅢ） hetero-metallic compound containing two kinds of ligands, namely [CuⅡ（H2pdc）（phen）（H2O）]（HⅢ3O）2[CeⅢ（pdc）3][CuⅡ（phen）Ce（pdc）3]（1, H2 pdc = pyridine-2,6-dicarboxylic acid, phe...A new 3d-4f（CuⅡ-CeⅢ） hetero-metallic compound containing two kinds of ligands, namely [CuⅡ（H2pdc）（phen）（H2O）]（HⅢ3O）2[CeⅢ（pdc）3][CuⅡ（phen）Ce（pdc）3]（1, H2 pdc = pyridine-2,6-dicarboxylic acid, phen = 1,10-phenanthroline）, has been synthesized by an ionothermal method using the ionic liquid 3-butyl-1-methylimidazolium bromide（[Bmim]Br） as solvent, and characterized by elemental analysis, energy-dispersive X-ray spectroscopy（EDS）, IR, XPS and single-crystal X-ray diffraction. The structure reveals that 1 belongs to the triclinic system, space group P1 with a = 12.044（7）, b = 14.841（8）, c = 22.305（13） A, α = 85.802（12）, β = 85.471（12）, γ = 89.174（11）°, Z = 2, V = 3964（4） A3, Dc = 1.804 g·cm-3, F（000） = 2140, μ = 1.757 mm-1, the final R = 0.0734, wR = 0.1094 and S = 1.013. The compound can be viewed as a two-dimensional layered structure composed by 3d-4f hetero-nuclear anions [Cu（phen）Ce（pdc）3]-, coordination cations [Cu（H2pdc）（phen）（H2O）]2＋, coordination anions [Ce（pdc）3]3- and protonated water molecules via hydrogen bonding interactions and π-π stacking. Moreover, the antimicrobial activities of 1 have been also investigated. The results indicated that its inhibitory activity is slightly higher than that of penicillin against Candida albicans.展开更多
Three sandwich-like[Ln_(2)Fe_(2)(B-α-FeW_9O_(34))_(2)]^(10-) clusters(Ln_(2)Fe_(4),Ln=Dy(1),Ho(2),and Y(3)) were obtained by reacting Na_9[B-α-SbW_9O_(33)],Ln_(2)O_(3),FeCl_(3)·6H_(2)O and KH_(2)PO_(4).The[B-α...Three sandwich-like[Ln_(2)Fe_(2)(B-α-FeW_9O_(34))_(2)]^(10-) clusters(Ln_(2)Fe_(4),Ln=Dy(1),Ho(2),and Y(3)) were obtained by reacting Na_9[B-α-SbW_9O_(33)],Ln_(2)O_(3),FeCl_(3)·6H_(2)O and KH_(2)PO_(4).The[B-α-FeW_9O_(34)]^(11-) units were formed via the in situ conversion of lacunary polyoxometalates(POM)[B-α-SbW_9O_(33)]^(9-)and the Ln^(3+)ions were generated from the slow dissolution of Ln_(2)O_(3),both of which play important roles in the synthesis of Ln_(2)Fe_(4).Ln_(2)Fe_(4) is the first 3d-4f cluster assembled from d-metal heteroatom-containing POM.The Dy_(2)Fe_(4) cluster exhibits single-molecule magnet properties with an 80 K energy barrier in an optimal DC field.Cyclic voltammetry tests and controlled-potential coulometry experiments show that the polyoxometalate Fe heteroatom in clusters 1-3 is also electrochemically active.展开更多
Two series of 3d-Gd mixed-metal phosphonate complexes with either only two gadolinium centers such as{Gd2},{Ni2Gd2},{Co4Gd2},{Co8Gd2},{Fe6Gd2},and{Fe17Gd2}or more than two gadoliniums such as{Co8Gd4},{Mn8Gd4},{Co4Gd6}...Two series of 3d-Gd mixed-metal phosphonate complexes with either only two gadolinium centers such as{Gd2},{Ni2Gd2},{Co4Gd2},{Co8Gd2},{Fe6Gd2},and{Fe17Gd2}or more than two gadoliniums such as{Co8Gd4},{Mn8Gd4},{Co4Gd6},{Mn4Gd6},{Co6Gd8},{Ni5Gd8},{Ni6Gd6},{Co8Gd8},and{Mn9Gd9}have been solvothermally prepared and magnetothermally studied.The nearly identical environments of the Gd(III)dimer in thefirst series allow us to qualitatively analyze the effect of magnetic exchange coupling on the magne-tocaloric effect(MCE).By doubling,tripling,or quadrupling of the Gd(III)centers,the second series of 3d-Gd mixed-metal complexes was built to further test the other effects of exchange couplings on MCE in more complicated circumstances.For the antiferromagnetic coupling cases,the results are nearly identical but diversify when topological spin frustrations are created,whose massive low-lying excited spin states help enhance MCE.For presumably ferromagnetically coupled ones,albeit are rare in phosphonate complexes,they do exhibit excellent MCE.Meanwhile,the com-plexes with weakly coupled metal centers serve as excellent examples for studying the effect of molecular mass on MCE when its magnitude is expressed in the unit of Joule per kilogram,from which we can see the values are directly proportional to the percentage of the Gd(III)ions in molecular weight.展开更多
Six novel 3D layer-pillared lanthanide-transition metal coordination polymers,LnCuX(IN)2(Ac)(H2O)(Ln = Tb,X = Br(1);Ln = Er,X = Cl(2)),[LnCuCl(IN)2(Ac)].H2O(Ln = Gd(3);Ln = Eu(4)),and [LnCu2Br2(IN)2(Ac)(H2O)].nH2O(Ln ...Six novel 3D layer-pillared lanthanide-transition metal coordination polymers,LnCuX(IN)2(Ac)(H2O)(Ln = Tb,X = Br(1);Ln = Er,X = Cl(2)),[LnCuCl(IN)2(Ac)].H2O(Ln = Gd(3);Ln = Eu(4)),and [LnCu2Br2(IN)2(Ac)(H2O)].nH2O(Ln = Dy,n =0(5);Ln = Gd,n = 0.5(6))(IN = isonicotinate,Ac = acetate),have been obtained by linking Ln-organic layers and diverse Cu-complex pillars under hydrothermal conditions.1 and 2 are isostructural and formed by 2D Ln-IN-Ac layers and CuX(IN)2 pillars(X = Br(1),X= Cl(2));3 and 4 are isomorphic and comprised of 2D Ln-IN-Ac layers and dimeric Cu2Cl(IN)4 pillars;while 5 and 6 are isostructural and built from 2D Ln-IN-Ac layers and tetrameric Cu4Br4(IN)4 pillars.The magnetic susceptibility investigation of 3 and 6 shows the presence of weak antiferromagnetic exchange interactions between the Ln3+ ions.Compounds 1-6 represent good examples of using 2D Ln-organic layers and diverse Cu-complex pillars as building units to construct intriguing 3D Ln-TM-organic frameworks.展开更多
It is a meaningful and challenging work for structural and synthetic chemists to isolate nano-sized high-nuclearity cluster-molecules.In this work,two largest hetero-metallic nano-clusters Gd_(158)Co_(38) were obtaine...It is a meaningful and challenging work for structural and synthetic chemists to isolate nano-sized high-nuclearity cluster-molecules.In this work,two largest hetero-metallic nano-clusters Gd_(158)Co_(38) were obtained via the“multi-anions-template”method.Different from the reported giant hollow-nano-clusters,the Ln_(158) core in Gd_(158)Co_(38)(the protein-sized nano-clusters,ca.4.3 nm×3.6 nm×3.5 nm)has the highest Ln nuclear number,which is integrated by twelve halide ions(with the form of icosahedron)as key templates,while Co ions(as 3d metals)are located in its periphery.This emergence indicates a novel structure form of non-open Ln-containing high-nuclearity clusters,and affords a consummate pattern to analyse and assemble the complex cluster-molecules.In addition,Gd_(158)Co_(38)@Cl_(12)breaks the record magnetic entropy change of 3d-4f clusters with−∆S_(m)^(max)=46.95 J kg^(−1)K^(−1)at 7.0 T,2.0 K.展开更多
基金Supported by the National Natural Science Foundation of China(5110208121072049)+1 种基金the University’s Science and Technology Innovation Team of Heilongjiang Province(2010td03)the Science and Technology Bureau of Heilongjiang Province(B201215)
基金Project supported by the Youth Project of Nanyang Normal University(No.QN2015027)
文摘A new 3d-4f（CuⅡ-CeⅢ） hetero-metallic compound containing two kinds of ligands, namely [CuⅡ（H2pdc）（phen）（H2O）]（HⅢ3O）2[CeⅢ（pdc）3][CuⅡ（phen）Ce（pdc）3]（1, H2 pdc = pyridine-2,6-dicarboxylic acid, phen = 1,10-phenanthroline）, has been synthesized by an ionothermal method using the ionic liquid 3-butyl-1-methylimidazolium bromide（[Bmim]Br） as solvent, and characterized by elemental analysis, energy-dispersive X-ray spectroscopy（EDS）, IR, XPS and single-crystal X-ray diffraction. The structure reveals that 1 belongs to the triclinic system, space group P1 with a = 12.044（7）, b = 14.841（8）, c = 22.305（13） A, α = 85.802（12）, β = 85.471（12）, γ = 89.174（11）°, Z = 2, V = 3964（4） A3, Dc = 1.804 g·cm-3, F（000） = 2140, μ = 1.757 mm-1, the final R = 0.0734, wR = 0.1094 and S = 1.013. The compound can be viewed as a two-dimensional layered structure composed by 3d-4f hetero-nuclear anions [Cu（phen）Ce（pdc）3]-, coordination cations [Cu（H2pdc）（phen）（H2O）]2＋, coordination anions [Ce（pdc）3]3- and protonated water molecules via hydrogen bonding interactions and π-π stacking. Moreover, the antimicrobial activities of 1 have been also investigated. The results indicated that its inhibitory activity is slightly higher than that of penicillin against Candida albicans.
基金supported by the National Natural Science Foundation of China(Nos.21871224,92161104,92161203 and 21721001)Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM No.RD2021040301)。
文摘Three sandwich-like[Ln_(2)Fe_(2)(B-α-FeW_9O_(34))_(2)]^(10-) clusters(Ln_(2)Fe_(4),Ln=Dy(1),Ho(2),and Y(3)) were obtained by reacting Na_9[B-α-SbW_9O_(33)],Ln_(2)O_(3),FeCl_(3)·6H_(2)O and KH_(2)PO_(4).The[B-α-FeW_9O_(34)]^(11-) units were formed via the in situ conversion of lacunary polyoxometalates(POM)[B-α-SbW_9O_(33)]^(9-)and the Ln^(3+)ions were generated from the slow dissolution of Ln_(2)O_(3),both of which play important roles in the synthesis of Ln_(2)Fe_(4).Ln_(2)Fe_(4) is the first 3d-4f cluster assembled from d-metal heteroatom-containing POM.The Dy_(2)Fe_(4) cluster exhibits single-molecule magnet properties with an 80 K energy barrier in an optimal DC field.Cyclic voltammetry tests and controlled-potential coulometry experiments show that the polyoxometalate Fe heteroatom in clusters 1-3 is also electrochemically active.
基金National Natural Science Foundation of China,Grant/Award Numbers:21971203,22375157State Key Laboratory of Electrical Insulation and Power Equipment,Grant/Award Numbers:EIPE23402,EIPE23405+3 种基金Special Support Plan of Shaanxi Province for Young Top-notch Talent and the Fundamental Research Funds for Central Universities,Grant/Award Number:xtr052023002Medical-Engineering Cross Project of the First Affiliated Hospital of XJTU,Grant/Award Number:QYJC02Spanish MICINN,Grant/Award Number:PID2021-124734OB-C21“Scientists+Engineers”Team Building Project of Qin Chuang Yuan,Grant/Award Number:2022KXJ-088。
文摘Two series of 3d-Gd mixed-metal phosphonate complexes with either only two gadolinium centers such as{Gd2},{Ni2Gd2},{Co4Gd2},{Co8Gd2},{Fe6Gd2},and{Fe17Gd2}or more than two gadoliniums such as{Co8Gd4},{Mn8Gd4},{Co4Gd6},{Mn4Gd6},{Co6Gd8},{Ni5Gd8},{Ni6Gd6},{Co8Gd8},and{Mn9Gd9}have been solvothermally prepared and magnetothermally studied.The nearly identical environments of the Gd(III)dimer in thefirst series allow us to qualitatively analyze the effect of magnetic exchange coupling on the magne-tocaloric effect(MCE).By doubling,tripling,or quadrupling of the Gd(III)centers,the second series of 3d-Gd mixed-metal complexes was built to further test the other effects of exchange couplings on MCE in more complicated circumstances.For the antiferromagnetic coupling cases,the results are nearly identical but diversify when topological spin frustrations are created,whose massive low-lying excited spin states help enhance MCE.For presumably ferromagnetically coupled ones,albeit are rare in phosphonate complexes,they do exhibit excellent MCE.Meanwhile,the com-plexes with weakly coupled metal centers serve as excellent examples for studying the effect of molecular mass on MCE when its magnitude is expressed in the unit of Joule per kilogram,from which we can see the values are directly proportional to the percentage of the Gd(III)ions in molecular weight.
基金supported by the National Natural Science Foundation of China(50872133)the National Natural Science Fund for Distinguished Young Scholars of China(20725101)+1 种基金the National Basic Research Program of China(2011CB932504)the Natural Science Foundation of Fujian Province(E0510030 & 2008F3120)
文摘Six novel 3D layer-pillared lanthanide-transition metal coordination polymers,LnCuX(IN)2(Ac)(H2O)(Ln = Tb,X = Br(1);Ln = Er,X = Cl(2)),[LnCuCl(IN)2(Ac)].H2O(Ln = Gd(3);Ln = Eu(4)),and [LnCu2Br2(IN)2(Ac)(H2O)].nH2O(Ln = Dy,n =0(5);Ln = Gd,n = 0.5(6))(IN = isonicotinate,Ac = acetate),have been obtained by linking Ln-organic layers and diverse Cu-complex pillars under hydrothermal conditions.1 and 2 are isostructural and formed by 2D Ln-IN-Ac layers and CuX(IN)2 pillars(X = Br(1),X= Cl(2));3 and 4 are isomorphic and comprised of 2D Ln-IN-Ac layers and dimeric Cu2Cl(IN)4 pillars;while 5 and 6 are isostructural and built from 2D Ln-IN-Ac layers and tetrameric Cu4Br4(IN)4 pillars.The magnetic susceptibility investigation of 3 and 6 shows the presence of weak antiferromagnetic exchange interactions between the Ln3+ ions.Compounds 1-6 represent good examples of using 2D Ln-organic layers and diverse Cu-complex pillars as building units to construct intriguing 3D Ln-TM-organic frameworks.
基金supported by the National Key R&D Program of China(2018YFA0306004)the National Natural Science Foundation of China(21571103,21973038)+1 种基金Jiangsu Province(BK20191359)the Joint Fund for Regional Innovation and Development(U20A2073)。
文摘It is a meaningful and challenging work for structural and synthetic chemists to isolate nano-sized high-nuclearity cluster-molecules.In this work,two largest hetero-metallic nano-clusters Gd_(158)Co_(38) were obtained via the“multi-anions-template”method.Different from the reported giant hollow-nano-clusters,the Ln_(158) core in Gd_(158)Co_(38)(the protein-sized nano-clusters,ca.4.3 nm×3.6 nm×3.5 nm)has the highest Ln nuclear number,which is integrated by twelve halide ions(with the form of icosahedron)as key templates,while Co ions(as 3d metals)are located in its periphery.This emergence indicates a novel structure form of non-open Ln-containing high-nuclearity clusters,and affords a consummate pattern to analyse and assemble the complex cluster-molecules.In addition,Gd_(158)Co_(38)@Cl_(12)breaks the record magnetic entropy change of 3d-4f clusters with−∆S_(m)^(max)=46.95 J kg^(−1)K^(−1)at 7.0 T,2.0 K.
