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
A new cyano-bridged complex Eu(DMSO)3(H2O)3Cr(CN)6·H2O with one-dimensional chain molecular structure was synthesized and characterized. The crystal data for the title complex: orthorhombic, P212121, a=0.972 2(3)...A new cyano-bridged complex Eu(DMSO)3(H2O)3Cr(CN)6·H2O with one-dimensional chain molecular structure was synthesized and characterized. The crystal data for the title complex: orthorhombic, P212121, a=0.972 2(3) nm, b=1.489 5(4) nm, c=1.748 6(5)nm, Z=4, μ=3.171 mm-1, final R1=0.020 4, wR2=0.043 4. From magnetic susceptibility measurements the complex was found to exhibit a weak ferromagnetic interaction between the Eu (III) and Cr(III) atoms. CCDC: 272212.展开更多
The design of assembling high-nuclearity transition-lanthanide(3d-4f) clusters along with excellent magnetocaloric effect(MCE) is one of the most prominent fields but is extremely challenging. Herein, two heterometall...The design of assembling high-nuclearity transition-lanthanide(3d-4f) clusters along with excellent magnetocaloric effect(MCE) is one of the most prominent fields but is extremely challenging. Herein, two heterometallic metal coordination polymers are constructed via the “carbonatetemplate” method, formulated as {[Gd_(18)Ni_(24)(IDA)_(22)(CO_(3))_(7)(μ_(3)-OH)_(32)(μ_(2)-OH)_(3)(H_(2)O)_(5)Cl]·Cl_(8)·(H_(2)O)_(14)}nand{[Eu_(18)Ni_(23.5)(IDA)_(22)(CO_(3)_(7)(μ_(3)-OH)_(32)(H_(2)O)_(5)(IN)(CH_(3)COO)_(2)(NH_(2)CH_(2)COO)Cl]·C_(l6)·(H_(2)O)_(17)}n[abbreviated as 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))n respectively;H_(2)IDA = iminodiacetic acid;HIN = isonicotinic acid]. Concerning the structures, compounds 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))nboth feature the one-dimensional(1D) chain-like structure which is rarely reported in high-nuclearity metal complexes. Meanwhile, the large presences of Gd3+ ions in compound 1-(Gd18Ni24)nare conducive to the fantastic MCE, and the value of-ΔS_(m)is 35.30 J kg^(-1)K^(-1) at 3.0 K and ΔH = 7.0 T. And more significantly, compound 1-Gd_(18)Ni_(24)n shows the large low-field magnetic entropy change(-ΔS_(m)= 20.95 J kg(-1) K(-1) at 2.0 K and ΔH = 2.0 T)among the published 3 d-4 f mixed metal clusters.展开更多
The title complex 1,{[CuEu（Hbidc）2（H2O）4]·H2O}n（H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Comple...The title complex 1,{[CuEu（Hbidc）2（H2O）4]·H2O}n（H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791（2）,b = 12.058（3）,c = 12.109（3）,α = 82.189（5）,β = 72.407（5）,γ = 89.184（4）°,V = 1073.7（5）3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ（MoKα） = 3.967 mm-1,F（000） = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I 2σ（I）.Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand（Hbidc）.Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.展开更多
(GdCa)(SiO)Oapatite crystals doped with different concentrations of Ce were synthesized by the Floating Zone(FZ) method, and we have evaluated the photoluminescence(PL) and radio luminescence(RL) properties. In PL, an...(GdCa)(SiO)Oapatite crystals doped with different concentrations of Ce were synthesized by the Floating Zone(FZ) method, and we have evaluated the photoluminescence(PL) and radio luminescence(RL) properties. In PL, an emission band appeared around 400 nm under excitation at 300 nm due to the5 d-4 f transitions of Ce3+. The PL decay curves were approximated by a second-order exponential decay function, and the derived decay time constants ranged around 20-25 ns and 40-480 ns. Similar emission was observed in RL, but the decay time constants were much longer than those in PL. The RL afterglow was the lowest in the 1.0% Ce-doped sample. The 1.0% and 2.0% Ce-doped samples showed a full-energy peak in the pulse height spectrum measured underAm 5.5 MeV α-ray irradiation, and the absolute scintillation light yields were estimated to be around 55 and 36 ph/5.5 MeV-a, respectively.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
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.
文摘A new cyano-bridged complex Eu(DMSO)3(H2O)3Cr(CN)6·H2O with one-dimensional chain molecular structure was synthesized and characterized. The crystal data for the title complex: orthorhombic, P212121, a=0.972 2(3) nm, b=1.489 5(4) nm, c=1.748 6(5)nm, Z=4, μ=3.171 mm-1, final R1=0.020 4, wR2=0.043 4. From magnetic susceptibility measurements the complex was found to exhibit a weak ferromagnetic interaction between the Eu (III) and Cr(III) atoms. CCDC: 272212.
基金supported by the Natural Science Foundation of China (No. 21571103)Jiangsu (No. BK20191359)the Project of Natural Science Foundation of the Higher Education Institutions of Anhui Province, China (No. KJ2019A0350)。
文摘The design of assembling high-nuclearity transition-lanthanide(3d-4f) clusters along with excellent magnetocaloric effect(MCE) is one of the most prominent fields but is extremely challenging. Herein, two heterometallic metal coordination polymers are constructed via the “carbonatetemplate” method, formulated as {[Gd_(18)Ni_(24)(IDA)_(22)(CO_(3))_(7)(μ_(3)-OH)_(32)(μ_(2)-OH)_(3)(H_(2)O)_(5)Cl]·Cl_(8)·(H_(2)O)_(14)}nand{[Eu_(18)Ni_(23.5)(IDA)_(22)(CO_(3)_(7)(μ_(3)-OH)_(32)(H_(2)O)_(5)(IN)(CH_(3)COO)_(2)(NH_(2)CH_(2)COO)Cl]·C_(l6)·(H_(2)O)_(17)}n[abbreviated as 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))n respectively;H_(2)IDA = iminodiacetic acid;HIN = isonicotinic acid]. Concerning the structures, compounds 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))nboth feature the one-dimensional(1D) chain-like structure which is rarely reported in high-nuclearity metal complexes. Meanwhile, the large presences of Gd3+ ions in compound 1-(Gd18Ni24)nare conducive to the fantastic MCE, and the value of-ΔS_(m)is 35.30 J kg^(-1)K^(-1) at 3.0 K and ΔH = 7.0 T. And more significantly, compound 1-Gd_(18)Ni_(24)n shows the large low-field magnetic entropy change(-ΔS_(m)= 20.95 J kg(-1) K(-1) at 2.0 K and ΔH = 2.0 T)among the published 3 d-4 f mixed metal clusters.
基金Supported by the Nanjing University of Posts and Telecommunications(No.NY209032)the National Natural Science Foundation of China(No.21001065)the Major State Basic Research Development Program of China (973 Program,No.2009CB930600)
文摘The title complex 1,{[CuEu（Hbidc）2（H2O）4]·H2O}n（H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791（2）,b = 12.058（3）,c = 12.109（3）,α = 82.189（5）,β = 72.407（5）,γ = 89.184（4）°,V = 1073.7（5）3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ（MoKα） = 3.967 mm-1,F（000） = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I 2σ（I）.Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand（Hbidc）.Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.
基金Project supported by a Grant-in-Aid for Scientific Research(A) 26249147 from the Ministry of Education,Culture,Sports,Science and Technology of Japan(MEXT)JST A-step,Cooperative Research Project of Research Institute of Electronics,Shizuoka University+1 种基金Inamori FoundationKRF Foundation
文摘(GdCa)(SiO)Oapatite crystals doped with different concentrations of Ce were synthesized by the Floating Zone(FZ) method, and we have evaluated the photoluminescence(PL) and radio luminescence(RL) properties. In PL, an emission band appeared around 400 nm under excitation at 300 nm due to the5 d-4 f transitions of Ce3+. The PL decay curves were approximated by a second-order exponential decay function, and the derived decay time constants ranged around 20-25 ns and 40-480 ns. Similar emission was observed in RL, but the decay time constants were much longer than those in PL. The RL afterglow was the lowest in the 1.0% Ce-doped sample. The 1.0% and 2.0% Ce-doped samples showed a full-energy peak in the pulse height spectrum measured underAm 5.5 MeV α-ray irradiation, and the absolute scintillation light yields were estimated to be around 55 and 36 ph/5.5 MeV-a, respectively.
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.
