Two 3d-4f-5d heterometallic cluster-containing polyoxometalates,formulated as Na_(22){(SbW_(9)O_(33))_(4)[La_(3)W_(6)MO_(18)(H_(2)O)_(8)(CH_(3)COO)_(4)]_(2)}·nH_(2)O(abbreviated as La_(6)M_(2),M=Co/Mn)were synthe...Two 3d-4f-5d heterometallic cluster-containing polyoxometalates,formulated as Na_(22){(SbW_(9)O_(33))_(4)[La_(3)W_(6)MO_(18)(H_(2)O)_(8)(CH_(3)COO)_(4)]_(2)}·nH_(2)O(abbreviated as La_(6)M_(2),M=Co/Mn)were synthesized and structurally characterized.Single-crystal X-ray diffraction analyses reveal that the polyanions of La_(6)Co_(2)and La_(6)Mn_(2)consist of the uncommon 3d-4f-5d clusters{La_(6)W_(12)Co_(2)}and{La_(6)W_(12)Mn_(2)},which are encapsulated by four trilacunary Keggin tungstoantimonates to form the parallelogram-shaped title compounds.Additionally,the polyanions can be extended into a two-dimensional(2D)frame by the linkage of peripheral Na+ions.The inner space of the 2D layer was filled with water molecules and thus an H-bonded network was formed,which is expected to exhibit a fascinating proton conductivity.The study of water-assisted proton conduction demonstrated that La_(6)Co_(2)and La_(6)Mn_(2)were temperature-and humiditydependent proton conductors,respectively,and the proton conductivities could reach 1.3×10^(-2)and 2.3×10^(-2)S/cm at 65℃and 90%RH conditions.展开更多
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
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
Benefitting from its unique NASICON-type framework,the Na_(3)V_(2)(PO_(4))_(3)(NVP)cathodes have aroused extensive interest and have been deemed as the promising cathode candidate for sodium-ion batteries(SIBs).Unfort...Benefitting from its unique NASICON-type framework,the Na_(3)V_(2)(PO_(4))_(3)(NVP)cathodes have aroused extensive interest and have been deemed as the promising cathode candidate for sodium-ion batteries(SIBs).Unfortunately,the poor electronic conductivity,combined with the undesirable volume variations,seriously hinders the practical application of NVP cathode,especially at low temperatures.Herein,a dual-strategy,F substitution accompanied by V vacancies and the construction of three-dimensional(3D)nitrogen-doped carbonaceous frameworks(NC),were employed for the NVP cathode(F-NVP/C@3DNC).The former can remarkably decrease the particle size and enhance Na^(+)migration capability,increasing the ionic conductivity.Meanwhile,the electronic connection and effective buffering can be obtained from the latter,strengthening the electrode integrity.Consequently,up to 100 cycles at 0.1 A g^(-1),a reversible capacity of 113.8 mAh g^(-1),approaching the theoretical value(117 mAh g^(-1)),is demonstrated,accompa-nied by impressive capacity retentions at 1.0(93.75%after 4800 cycles)and 20.0 A g^(-1)(92.7%after 1000 cycles).More importantly,even at-20℃,a superior specific capacity(102.6 mAh g^(-1) after 100 cycles at 0.1 A g^(-1))and high capacity retention(86.6%at 20.0 A g^(-1) up to 1000 cycles)can still be obtained simul-taneously.Significantly,the design of F-NVP/C@3DNC provides insights for the fabrication of polyanion cathodes for applications at low temperatures with modified structure stability and reaction kinetics.展开更多
基金supported by the National Natural Science Foundation of China(No.22071045)the Excellent Youth Science Fund Project of Henan Province(No.202300410042)+2 种基金the Natural Science Foundation of Henan Province(No.232300420372)Henan Universitythe State Key Laboratory of Physical Chemistry of the Solid Surface of Xiamen University。
文摘Two 3d-4f-5d heterometallic cluster-containing polyoxometalates,formulated as Na_(22){(SbW_(9)O_(33))_(4)[La_(3)W_(6)MO_(18)(H_(2)O)_(8)(CH_(3)COO)_(4)]_(2)}·nH_(2)O(abbreviated as La_(6)M_(2),M=Co/Mn)were synthesized and structurally characterized.Single-crystal X-ray diffraction analyses reveal that the polyanions of La_(6)Co_(2)and La_(6)Mn_(2)consist of the uncommon 3d-4f-5d clusters{La_(6)W_(12)Co_(2)}and{La_(6)W_(12)Mn_(2)},which are encapsulated by four trilacunary Keggin tungstoantimonates to form the parallelogram-shaped title compounds.Additionally,the polyanions can be extended into a two-dimensional(2D)frame by the linkage of peripheral Na+ions.The inner space of the 2D layer was filled with water molecules and thus an H-bonded network was formed,which is expected to exhibit a fascinating proton conductivity.The study of water-assisted proton conduction demonstrated that La_(6)Co_(2)and La_(6)Mn_(2)were temperature-and humiditydependent proton conductors,respectively,and the proton conductivities could reach 1.3×10^(-2)and 2.3×10^(-2)S/cm at 65℃and 90%RH conditions.
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support from the faculty startup funds from the Yangzhou University,the Natural Science Foundation of Jiangsu Province (Grant No.BK20210821)the National Natural Science Foundation of China (Grant No.21978251)the Lvyangjinfeng Talent Program of Yangzhou.
文摘Benefitting from its unique NASICON-type framework,the Na_(3)V_(2)(PO_(4))_(3)(NVP)cathodes have aroused extensive interest and have been deemed as the promising cathode candidate for sodium-ion batteries(SIBs).Unfortunately,the poor electronic conductivity,combined with the undesirable volume variations,seriously hinders the practical application of NVP cathode,especially at low temperatures.Herein,a dual-strategy,F substitution accompanied by V vacancies and the construction of three-dimensional(3D)nitrogen-doped carbonaceous frameworks(NC),were employed for the NVP cathode(F-NVP/C@3DNC).The former can remarkably decrease the particle size and enhance Na^(+)migration capability,increasing the ionic conductivity.Meanwhile,the electronic connection and effective buffering can be obtained from the latter,strengthening the electrode integrity.Consequently,up to 100 cycles at 0.1 A g^(-1),a reversible capacity of 113.8 mAh g^(-1),approaching the theoretical value(117 mAh g^(-1)),is demonstrated,accompa-nied by impressive capacity retentions at 1.0(93.75%after 4800 cycles)and 20.0 A g^(-1)(92.7%after 1000 cycles).More importantly,even at-20℃,a superior specific capacity(102.6 mAh g^(-1) after 100 cycles at 0.1 A g^(-1))and high capacity retention(86.6%at 20.0 A g^(-1) up to 1000 cycles)can still be obtained simul-taneously.Significantly,the design of F-NVP/C@3DNC provides insights for the fabrication of polyanion cathodes for applications at low temperatures with modified structure stability and reaction kinetics.