Iron overload has been evidenced to contribute to obesity-associated metabolic disorders,including insulin resistance.Strategies to reduce iron levels might help manage the metabolic complications associated with obes...Iron overload has been evidenced to contribute to obesity-associated metabolic disorders,including insulin resistance.Strategies to reduce iron levels might help manage the metabolic complications associated with obesity.Here,it is demonstrated that the specific accumulation of oleic acid-modified polyoxovanadates(OPOVs)in adipose tissue leads to the reduction of iron concentrations in adipocytes in mice fed with a high-fat diet(HFD).Conjugation of oleic acids to polyoxovanadates enables tissue-specific depletion of iron from white adipose tissue(WAT)by OPOVs,protecting mice from HFD-induced obesity and obesity-associated metabolic deteriorations.Glucose tolerance and insulin sensitivity are improved in OPOV-treated mice,which demonstrates that the OPOV-induced iron depletion can reverse the metabolic degeneration caused by HFD-induced obesity.Furthermore,a decrease in expression of the marker genes of iron overload suggests the participation of OPOVs in maintaining iron homeostasis and a potential medical application of vanadium clusters in targeting the iron overload caused by obesity.These findings underscore the potential of vanadate-based clusters tailored to address the complex interplay between iron metabolism and metabolic health.展开更多
The polyoxovanadate（NH4）7[MnV13O38]（AMV） was synthesized and characterized by X-ray diffraction pattern, Fourier transform infrared spectra, and field emission scanning electron microscope equipped with energy dis...The polyoxovanadate（NH4）7[MnV13O38]（AMV） was synthesized and characterized by X-ray diffraction pattern, Fourier transform infrared spectra, and field emission scanning electron microscope equipped with energy dispersive X-ray spectroscopy. In order to improve the electrochemical performance of AMV, the particle size of as-prepared AMV is decreased to nanoscale by re-precipitation in the water-ethanol solution. The results of the electrochemical impedance spectra and the 4-pin probe measurements show that the electrical conductivity of AMV is improved by decreasing the particle size. The nanoparticle AMV shows higher initial discharge capacity and energy density than the as-prepared AMV when cycled at 0.5C. On the other hand, the nanoparticle AMV exhibits higher rate capability than the as-prepared AMV.展开更多
Obesity,characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs,is frequently accompanied by chronic low-grade inflammation.As long-acting insulin sensitizers,the organically-...Obesity,characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs,is frequently accompanied by chronic low-grade inflammation.As long-acting insulin sensitizers,the organically-derivatized polyoxovanadates(POVs),can extend the dosing interval of antidiabetic drugs from hourly to almost daily.In this work,the protective activity of POVs is investigated by an eight-week in vivo experiment,in which a small amount of POVs was administrated orally to a mouse model of dietinduced obesity every day.The present study shows that administration of POVs significantly decreases the body weight of mice,reduces adipose tissue accumulation,and simultaneously reduces adipose tissue inflammation.In addition,the anti-obesogenic population of i NKT cells is protected potentially by POVs,which subsequently alleviates visceral adipose tissue inflammation in high-fat-diet(HFD)-fed mice against diet-induced obesity.By contrast,the change in body weight after POV treatment is the result of a substantial reduction in fat mass,with no obvious effects on lean body mass.These findings demonstrate that supplementary of POVs would be an effective way to combat obesity and metabolic disorders while lowering metabolic inflammation.展开更多
Polyoxovanadate-based MOFs microsphere electrode material, [Ni_2(4,4?-bipyridine)_3(H_2O)_2V_4O_(12)]·2.5 H_2O, was synthesized through a simple hydrothermal method, and then characterized through FT-IR, XRD and ...Polyoxovanadate-based MOFs microsphere electrode material, [Ni_2(4,4?-bipyridine)_3(H_2O)_2V_4O_(12)]·2.5 H_2O, was synthesized through a simple hydrothermal method, and then characterized through FT-IR, XRD and SEM. Electrochemical properties of the sample as supercapacitor electrodes in aqueous electrolyte were developed and studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy techniques. Results showed that a high specific capacitance of 152.36 F g^(-1) at current density of 1 A g^(-1) in 2 M KOH electrolyte, and 97.62% retention after 2500 charge-discharge cycles at current density of 4 A g^(-1), which is promising for applications in supercapacitors.展开更多
A new polyoxovanadate cluster, [NH_3(CH_2)_2NH_2(CH_2)_2NH_3]_4[VⅤ_6VⅣ_ 12O_ 42(PO_4)](PO_4)·2H_2O, has been synthesized and characterized by means of elemental analysis, IR spectrometry, EPR spectrometry, TG a...A new polyoxovanadate cluster, [NH_3(CH_2)_2NH_2(CH_2)_2NH_3]_4[VⅤ_6VⅣ_ 12O_ 42(PO_4)](PO_4)·2H_2O, has been synthesized and characterized by means of elemental analysis, IR spectrometry, EPR spectrometry, TG analysis and single crystal X-ray diffraction. This compound crystallizes in a monoclinic space group C2/c with a= 2.3912(5) nm, b=1.3002(3) nm, c=2.0172(4) nm, β=105.75(3)°, V=6.036(2) nm3, Z=2, R_1=0.0572, wR_2=0.1476. It has a superKeggin structure with a Keggin unit capped by six [VO_5] moieties on the pits on every side of the Keggin unit. The anti-tumor activity of the compound was estimated in three human tumor cell lines in vitro.展开更多
A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high ...A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high stability,weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design.In this endeavor,a ligand-dominated strategy that embodies tunable electrostatic repulsion andπ···πstacking was first employed to shape polyoxovanadate-based metal-organic polyhedra(VMOPs).Structural evolution involving transformation,interlock,and discovery of an unprecedented prototype of the Star of David was hence achievable.Not only as a handy tool for the primary structural control over VMOPs,these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors,representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.展开更多
A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （t...A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （tris（hydroxymethyl）aminomethane） and H2O in the molar ratio of 3：1：1：0.5：2.5：1400. Compound 1 crystallizes in the space group P42212 of the tetragonal system with a = b = 21.5009（8）, c = 28.401（2） A, V= 13129.5（12） A^3 Z = 4, Dc = 1.800 g/cm^3, μ（MoKa） = 1.932 mm^-1, λ（MoKa） = 0.71073 A, F（000） = 7063.4, C120H81.20ClCu5N20O38.7V15.35, Mr = 3557.58, the final R = 0.0594 and wR= 0.1320 for 7761 observed reflections （I 〉 2σ（I））. Structure analysis shows that 1 exhibits a 3D channel framework formed by the supramolecular assembly of Cu complexes and polyoxovanadate clusters via intermolecular hydrogen bonding, and the channels contain Cu complexes. Other characterizations by elemental analysis, XPS, IR, XRD and thermal analysis are also described.展开更多
A new compound has been synthesized under hydrothermal conditions and characterized by IR, elemental analysis, XPS and single-crystal X-ray diffraction analysis. The title compound [Mn（en）3]2en0.5[HV8VV8IVO38（CI）]...A new compound has been synthesized under hydrothermal conditions and characterized by IR, elemental analysis, XPS and single-crystal X-ray diffraction analysis. The title compound [Mn（en）3]2en0.5[HV8VV8IVO38（CI）]·4.5H2O crystallizes in monoclinic, space group C2/c, with a = 17.016（4）, b = 18.858（4）, c = 18.872（4） A, β = 93.667（4）°, V = 6043（2）A3, Z = 4, Dc = 2.242 g/cm3, Mr = 2040.12, F（000） = 4020,μ = 2.895 mm-1, Rint = 0.0921, R = 0.0649 and wR = 0.1325. Single-crystal X-ray structure analysis indicates that the title compound consists of a polyanion [HV8VV8IVO38（CI）]4- cage, two [Mn（en）3]2^2＋ cations, four and a half lattice waters and a half ethylenediamine. In addition, intermolecular O-H...N, O-H...O, N-H...O and C-H...O hydrogen bonds link the molecules together to form a three-dimensional structure.展开更多
The design and synthesis of high-nuclear polyoxometalates(POMs)utilizing secondary building blocks(SBB)is attractive and challenging.Herein,four new high-nuclear polyoxovanadates(POVs),{V_(20)S_(2)In_(42)P_(12)(CO_(2)...The design and synthesis of high-nuclear polyoxometalates(POMs)utilizing secondary building blocks(SBB)is attractive and challenging.Herein,four new high-nuclear polyoxovanadates(POVs),{V_(20)S_(2)In_(42)P_(12)(CO_(2))}(1),{V_(20)Mo_(2)In_(4)P_(12)(C_(2)O_(4))_(2)}(2),{V_(12)P_(6)SPb_(2)}(3)and{V_(12)P_(6)SCd_(2)}(4),were successfully synthesized under solvothermal conditions by incorporating transition metals into POVs.All the structures are constructed from the tetragonal{V_(5)(PhPO_(3))_(4)}SBB,wherein five{VO_(5)}square pyramids are interconnected by edge-sharing modes,and four phenylphosphonic acid ligands further coordinate with vanadium cations.Compounds 1 and 2 have similar structures in which two{V_(10)(PhPO_(3))_(6)(SO_(4))In_(2)}or{V_(10)(PhPO_(3))_(6)(MoO_(4))In_(2)}clusters are bridged by formate or oxalate ligands.While compounds 3 and 4 are constructed from{V_(12)(PhPO_(3))_(6)(SO_(4))}cluster doped with transition metals Pb or Cd.Notably,compound 4 demonstrated efficient catalytic activity for sulfide oxidation.展开更多
Precise control over metal-organic polyhedra(MOPs)architectures via metal and organic linker engineering presents a critical challenge for advancing functional porous materials with specific properties.The rational de...Precise control over metal-organic polyhedra(MOPs)architectures via metal and organic linker engineering presents a critical challenge for advancing functional porous materials with specific properties.The rational design of organic linkers and secondary building units(SBUs)with programmable configurational features facilitates the assembly of novel MOPs,wherein structural complexity is enhanced through the integration of low-symmetry linkers and expandable SBUs.Herein,a series of polyoxovanadatebased metal-organic polyhedra(VMOPs)with modulated structures were systematically engineered through linker desymmetrization and SBU expansion approach.Two types of tritopic triazine(D_(3h))-or imidazole(C_(s)/C_(1))-functionalized carboxylate ligands assemble with 3-connected prototype{V_(6)S}or expansional{V_(6)P}clusters,yielding VMOPs that exhibit structural evolution from T_(d)-symmetric regular tetrahedrons to D_(2d)-symmetric isosceles variants.Expansion of vertex clusters leads to structural fine-tuning of VMOPs,giving rise to diverse ligand conformations.Interestingly,these VMOPs exhibit significant differences during the iodine adsorption in both n-hexane solution and gaseous phases,which can be explained by the comprehensive influence of their cavity volume,the functional groups included,and the stacking arrangement.These findings demonstrate an effective structure-designing strategy via regulation of ligand symmetry and SBU architectural features,providing a powerful approach for the customized synthesis of MOPs with tailored structures and functionalities.展开更多
A new polyoxovanadate-based framework material[Cu(en)_(2)]_(4)V_(18)O_(42)(H_(2)O)·6H_(2)O(1)was designed and synthesized by hydrothermal reaction of NaVO_(3),Cu(NO_(3))_(2)·6H_(2)O and 1,2-diaminoethane(en)...A new polyoxovanadate-based framework material[Cu(en)_(2)]_(4)V_(18)O_(42)(H_(2)O)·6H_(2)O(1)was designed and synthesized by hydrothermal reaction of NaVO_(3),Cu(NO_(3))_(2)·6H_(2)O and 1,2-diaminoethane(en)via carefully adjusting the pH value of the reaction system.The structure of the title compound has been determined by single-crystal X-ray diff raction analysis,thermogravimetric analysis,infrared spectra and elemental analysis.Detail structural analysis demonstrate the three-dimensional(3D)framework structure of compound 1,which was composed of the[V_(18)O_(42)(H_(2)O)]_(8)−({V_(18)O_(42)(H_(2)O)})anions linked by the Cu^(2+)cations.Compound 1 represents the fi rst 3D framework based on{V_(18)O_(42)(H_(2)O)}polyoxoanions and copper complexes.Solar-driven degradation of residual organic pollutants in industrial wastewater is still a major problem for human beings.Photocatalytic experiments reveal that compound 1 possesses of excellent photocatalytic activity for the degradation of methylene blue and rhodamine B.展开更多
A novel polyoxovanadate-based MOFs microsphere,[Ni(phen)V2O7]·H2O(phen=1,10-phenanthroline),constructed from 3-D discrete nano-sheets has been prepared and characterized by XRD,FT-IR,SEM and TEM.Electrochemical p...A novel polyoxovanadate-based MOFs microsphere,[Ni(phen)V2O7]·H2O(phen=1,10-phenanthroline),constructed from 3-D discrete nano-sheets has been prepared and characterized by XRD,FT-IR,SEM and TEM.Electrochemical properties as supercapacitor of the as-prepared sample,such as CV,EIS,GCD and the cycle life test have also been studied.The as-prepared MOF(V,Ni)showed a high specific capacitance of 178.09 F×g^(-1) at 1 A×g^(-1) as well as good cycling stability and coulombic efficiency.This work proved that the novel MOFs based on polyoxovanadate hybrid material may serve as a promising electrode material for high-performance supercapacitor.展开更多
A novel organic-inorganic hybrid polyoxovanadate, [Ni（bpp）2]2（V4O12） （bpp= 1,3-bi-4-pyridylpropane）, was hydrothermally synthesized from a mix.ture of NiCl2＊6H2O, NH4VO3, bpp, EtOH and H2O. The crystal structur...A novel organic-inorganic hybrid polyoxovanadate, [Ni（bpp）2]2（V4O12） （bpp= 1,3-bi-4-pyridylpropane）, was hydrothermally synthesized from a mix.ture of NiCl2＊6H2O, NH4VO3, bpp, EtOH and H2O. The crystal structure consists of ∞^2[Ni（bpp）2]^2＋, two-dimensional networks interpenetrating perpendicularly with each other, and （V4O12）^4-, cyclic tetranuclear clusters linking the ∞^2[Ni（bpp）2]^2＋ networks to form a three-dimensional coordination framework. The crystal belongs to tetragonal space group I41/a with unit cell parameters, a= 2.14705 nm, c= 1.29293 nm. UV-Vis-NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 2.70 eV.展开更多
Three novel polyoxovanadate-based metal-organic frameworks(POV-MOFs),[Co_(2)(1,4-dtzb)_(3)]{V_(4)O_(12)}(V-Co-MOF_(1),1,4-dtzb=1,4-di(4H-1,2,4-triazol-4-yl)benzene],[Co_(3)(1,3-dtzb)_(2)][{V_(6)O_(18)}(V-Co-MOF_(2),1,...Three novel polyoxovanadate-based metal-organic frameworks(POV-MOFs),[Co_(2)(1,4-dtzb)_(3)]{V_(4)O_(12)}(V-Co-MOF_(1),1,4-dtzb=1,4-di(4H-1,2,4-triazol-4-yl)benzene],[Co_(3)(1,3-dtzb)_(2)][{V_(6)O_(18)}(V-Co-MOF_(2),1,3-dtzb=1,3-di(4H-1,2,4-triazol-4-yl)benzene],[Co_(4)(4,4’-bdtzb)_(2)]{V_(8)O_(24)}(V-Co-MOF_(3),4,4’-bdtzb=4,4’-(1,1’-biphenyl)-4,4’-diylbis(4H-1,2,4-triazole)benzene]were facilely synthesized and structurally characterized.Single-crystal X-ray diffraction analysis indicates that all the POV-MOFs possess open V sites lined on POV clusters of{V_(4)O_(12)}/{V_(6)O_(18)}/{V_(8)O_(24)}that uniformly distribute on the robust three-dimensional frameworks.This unique structural feature allows them to show high performance for sulfidesulfoxide transformation when performing the reaction in MeOH at 50℃ for 45 min using H_(2)O_(2) as green oxidant.Notably,V-Co-MOF1 exhibited the highest catalytic efficiency,with a conversion>99% and selectivity up to 97% for a series of sulfide substrates.Control reaction demonstrated the catalytically active centers are the open V sites while the MOF skeleton constructed from Co^(2+)and ligands also contributes to enhance the conversion and selectivity via synergistic effect.Furthermore,V-Co-MOF1 can be used as a stable heterogeneous catalyst,and both the structural integrity and catalytic performance were well reserved after five cycles,demonstrating their great potential for advanced catalytic oxidation.展开更多
Aqueous zinc-ion batteries(ZIBs)are attaining increasing attention for their high safety and low cost.Despite significant progresses in realizing high-performance cathode material for ZIBs,simultaneously endowing them...Aqueous zinc-ion batteries(ZIBs)are attaining increasing attention for their high safety and low cost.Despite significant progresses in realizing high-performance cathode material for ZIBs,simultaneously endowing them with high capacity and fast-charging capability,the long-term cycling stability remains a major unsolved challenge.In this work,a polyoxovanadate cluster of(NH_(4))_(8)[V_(19)O_(41)(OH)_(9)]·11H_(2)O(NOV)is defined as a cathode material for ZIBs that contains mixed-valence vanadium sites(V^(4+)and V^(5+)).A maximum of 26 electrons can be accommodated in one[V_(19)O_(41)(OH)_(9)]^(8-){V_(19)O_(50)}cluster,contributing to the high theoretical specific capacity of 328 mA·h·g^(-1).The Ti_(3)C_(2)T_(x) MXene nanosheets are incorporated into NOV with the help of ionic liquid(IL)linkers to restrain the dissolution of vanadium species and facilitate electron transport across the electrode.The interfacial bonding,anion exchange,and electrostatic interactions among NOV and MXene are provided by IL liquid.The nanohybrid of NOV-IL-MXene endows excellent contact between MXene and NOV,thereby enhanced charge transfer is observed at interface.Subsequently,the as-synthesized NOV-IL-MXene cathodes exhibit high discharge capacity of 413 mA·h·g^(-1) at 0.2 A·g^(-1) even at high mass loading of 5.2 mg·cm^(-2),remarkable rate performance of 182 mA·h·g^(-1) at 10 A·g^(-1),and impressive cycling stability of 94%capacity retention after 2000 cycles.This work opens up new opportunities to develop advanced polyoxovanadate hybrid cathodes for low-cost and high-performance aqueous ZIBs.展开更多
Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based hi...Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials.Herein we report the synthesis of sulfonate-functionalized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node.MOPs 1 and 2 exhibit octahedral cage configuration constructed from{V_(5)O_(9)Cl}vertex and 5-sulfoisophthalate linker.Owing to the ordered packing of octahedral cages along three axes,3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2.Coupled with the proton-conductive{V_(5)O_(9)Cl}vertexs as well as protonated counterions,an extensive H-bonded network is therefore generated for facile proton transfer.2 exhibits high proton conductivity of 3.02×10^(-2)S cm^(-1)at 65℃under 90%RH,recording the highest value for MOPs pellet sample.This value is enhanced~1order of magnitude compared with that of carboxylate-functionalized analogue 3,clearly illustrating the advantage of combining linker and metal cluster node for enhanced proton conduction.This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.展开更多
Multifunctional compatible stealth materials have emerged as the focal point of contemporary protection technology research and vanadium-based nanomaterials play a pivotal role in the development of advanced stealth m...Multifunctional compatible stealth materials have emerged as the focal point of contemporary protection technology research and vanadium-based nanomaterials play a pivotal role in the development of advanced stealth materials.Here,a compatible stealth aerogel is successfully synthesized by employing mixed-valence decavanadate as the vanadium oxide(VO_(x))molecular model.Ultralight{V^(Ⅳ)VV_(9)}/MXene aerogel(0.0429 g cm^(-3))exhibits exceptional radar stealth performance with a minimal reflection loss(RL_(min))of−57.74 dB(99.9998%EMW absorption)and a significantly superior radar cross section reduction value of 26.77 dB m2.The aerogel’s exceptional properties,including a low infrared(IR)emissivity(0.479)and a low thermal conductivity of(32.30 mW m^(-1)K^(-1)),are crucial for enabling compatibility with IR and thermal stealth technologies.The presence of a mixed-valence polyoxovanadate cluster leads to an increase in the Schottky barrier and enhances magnetic properties,consequently boosting interfacial polarization and contributing to magnetic losses during electromagnetic wave(EMW)absorption.Consequently,altering the number of valence electrons significantly enhances the compatible stealth capabilities.These findings contribute significantly to our comprehension of how microstructure impacts EMW absorption processes and provide a basis for further research into the development of VO_(x)-based compatible stealth materials.展开更多
Polyoxovanadates(POVs)are widely used in various fields,making it crucial to understand the electronic properties for their optimal applications.In this study,the electronic structures of fully-oxidized vanadate anion...Polyoxovanadates(POVs)are widely used in various fields,making it crucial to understand the electronic properties for their optimal applications.In this study,the electronic structures of fully-oxidized vanadate anions[V_(n)O_(m)]^(3-/4-)(n=1–5,m=4,7,9,12,14),including[VO_(4)]^(3-),[V_(2)O_(7)]^(4-),[V_(3)O_(9)]^(3-),[V_(4)O_(12)]^(4-),and[V_(5)O_(14)]^(3-),were investigated using density functional theory(DFT)calculations.A comprehensive analysis was conducted on the bond lengths,Wiberg bond index(WBI),bond critical points(BCPs),and covalent composition of these vanadates.The interaction between V―O_(t)and V―O_(b)in studied[V_(n)O_(m)]^(3-/4-)can be viewed as the combination of covalent bond and ionic bond.With an increase in the number of vanadium atoms,the V―O bond lengths decrease,while the covalent composition of V―O bonds increase.In addition,the covalent components of V―O_(t)are larger than those of corresponding V―O_(b).The analysis on charge density indicates that the charge density of cluster decreases as the size of the clusters increases,resulting in a corresponding increase in stability.This study enhances the understanding of the electronic properties of POVs,and the trends indentified are expected to provide valuable information for applications of POVs.展开更多
The reactions of the four-coordinated macrocyclic copper complex [CuL]（ClO4）2（L = 1,4,8,11-tetraazacyclotetradecane） with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO...The reactions of the four-coordinated macrocyclic copper complex [CuL]（ClO4）2（L = 1,4,8,11-tetraazacyclotetradecane） with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O（1）, [CuL]3[V（10）O（28）]·8H2O（2） and [Cu L]3[V6O（18）]·8H2O（3）. Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O（18）]6- ring, [V（10）O（28）]6- cluster, and [V（12）O（35）]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2＋ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O（18）]^6- rings in 1 and [V（12）O（35）]^10- rings in 3 into three-dimensional frameworks, respectively.展开更多
Compound [V_ 16 O_ 38 (Cl)][Cu(enMe)_2]_ 3.5 ·2H_2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction,elemental analysis,IR,EPR and TGA analysis. The X-ray c...Compound [V_ 16 O_ 38 (Cl)][Cu(enMe)_2]_ 3.5 ·2H_2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction,elemental analysis,IR,EPR and TGA analysis. The X-ray crystallography shows that compound 1 contains a new {V_ 16 O_ 38 } cluster shell,which is connected by [Cu(enMe)_2] 2+ coordination fragments into a 3-D framework. The compound crystallized in a monoclinic system with space group P2(1)/n,M =2235.82,a =1.26076(3) nm,b =2.55802(6) nm,c =2.14742(4) nm,β =90.7380(10)°, V =6.9250(3) nm 3,Z =4,F (000)=4418,D _c=2.145 g·cm -3 , μ =3.227 mm -1 ,( Δ/σ )=0.000,S =1.066.展开更多
基金supported by the National Natural Science Foundation of China(No.22101086)Guangzhou Basic and Applied Basic Research Project(No.202201010052)Guangdong Basic and Applied Basic Research Foundation(No.2023A1515140030).
文摘Iron overload has been evidenced to contribute to obesity-associated metabolic disorders,including insulin resistance.Strategies to reduce iron levels might help manage the metabolic complications associated with obesity.Here,it is demonstrated that the specific accumulation of oleic acid-modified polyoxovanadates(OPOVs)in adipose tissue leads to the reduction of iron concentrations in adipocytes in mice fed with a high-fat diet(HFD).Conjugation of oleic acids to polyoxovanadates enables tissue-specific depletion of iron from white adipose tissue(WAT)by OPOVs,protecting mice from HFD-induced obesity and obesity-associated metabolic deteriorations.Glucose tolerance and insulin sensitivity are improved in OPOV-treated mice,which demonstrates that the OPOV-induced iron depletion can reverse the metabolic degeneration caused by HFD-induced obesity.Furthermore,a decrease in expression of the marker genes of iron overload suggests the participation of OPOVs in maintaining iron homeostasis and a potential medical application of vanadium clusters in targeting the iron overload caused by obesity.These findings underscore the potential of vanadate-based clusters tailored to address the complex interplay between iron metabolism and metabolic health.
文摘The polyoxovanadate（NH4）7[MnV13O38]（AMV） was synthesized and characterized by X-ray diffraction pattern, Fourier transform infrared spectra, and field emission scanning electron microscope equipped with energy dispersive X-ray spectroscopy. In order to improve the electrochemical performance of AMV, the particle size of as-prepared AMV is decreased to nanoscale by re-precipitation in the water-ethanol solution. The results of the electrochemical impedance spectra and the 4-pin probe measurements show that the electrical conductivity of AMV is improved by decreasing the particle size. The nanoparticle AMV shows higher initial discharge capacity and energy density than the as-prepared AMV when cycled at 0.5C. On the other hand, the nanoparticle AMV exhibits higher rate capability than the as-prepared AMV.
基金supported by the National Natural Science Foundation of China(Nos.22101086,and 21225103)Natural Science Foundation of Guangdong Province(No.2021A1515010271)+1 种基金Tsinghua University Initiative Foundation Research Program(No.20131089204)the State Key Laboratory of Natural and Biomimetic Drugs(No.K20160202)。
文摘Obesity,characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs,is frequently accompanied by chronic low-grade inflammation.As long-acting insulin sensitizers,the organically-derivatized polyoxovanadates(POVs),can extend the dosing interval of antidiabetic drugs from hourly to almost daily.In this work,the protective activity of POVs is investigated by an eight-week in vivo experiment,in which a small amount of POVs was administrated orally to a mouse model of dietinduced obesity every day.The present study shows that administration of POVs significantly decreases the body weight of mice,reduces adipose tissue accumulation,and simultaneously reduces adipose tissue inflammation.In addition,the anti-obesogenic population of i NKT cells is protected potentially by POVs,which subsequently alleviates visceral adipose tissue inflammation in high-fat-diet(HFD)-fed mice against diet-induced obesity.By contrast,the change in body weight after POV treatment is the result of a substantial reduction in fat mass,with no obvious effects on lean body mass.These findings demonstrate that supplementary of POVs would be an effective way to combat obesity and metabolic disorders while lowering metabolic inflammation.
基金supported by the Natural Science Foundation of Fujian Province(No.2017J01420)
文摘Polyoxovanadate-based MOFs microsphere electrode material, [Ni_2(4,4?-bipyridine)_3(H_2O)_2V_4O_(12)]·2.5 H_2O, was synthesized through a simple hydrothermal method, and then characterized through FT-IR, XRD and SEM. Electrochemical properties of the sample as supercapacitor electrodes in aqueous electrolyte were developed and studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy techniques. Results showed that a high specific capacitance of 152.36 F g^(-1) at current density of 1 A g^(-1) in 2 M KOH electrolyte, and 97.62% retention after 2500 charge-discharge cycles at current density of 4 A g^(-1), which is promising for applications in supercapacitors.
文摘A new polyoxovanadate cluster, [NH_3(CH_2)_2NH_2(CH_2)_2NH_3]_4[VⅤ_6VⅣ_ 12O_ 42(PO_4)](PO_4)·2H_2O, has been synthesized and characterized by means of elemental analysis, IR spectrometry, EPR spectrometry, TG analysis and single crystal X-ray diffraction. This compound crystallizes in a monoclinic space group C2/c with a= 2.3912(5) nm, b=1.3002(3) nm, c=2.0172(4) nm, β=105.75(3)°, V=6.036(2) nm3, Z=2, R_1=0.0572, wR_2=0.1476. It has a superKeggin structure with a Keggin unit capped by six [VO_5] moieties on the pits on every side of the Keggin unit. The anti-tumor activity of the compound was estimated in three human tumor cell lines in vitro.
基金financially supported by the National Natural Science Foundation of China(No.22001066)the Natural Science Foundation of Hunan Province(Nos.2021JJ40049 and 2022JJ20007)+3 种基金the Science and Technology Innovation Program of Hunan Province(No.2022RC1115)J.Du acknowledges the Science and Technology Project of Hebei Education Department(No.QN2023049)Science Foundation of Hebei Normal University(No.L2023B51)TianHe-2(LvLiang,China)Cloud Computing Center for support。
文摘A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high stability,weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design.In this endeavor,a ligand-dominated strategy that embodies tunable electrostatic repulsion andπ···πstacking was first employed to shape polyoxovanadate-based metal-organic polyhedra(VMOPs).Structural evolution involving transformation,interlock,and discovery of an unprecedented prototype of the Star of David was hence achievable.Not only as a handy tool for the primary structural control over VMOPs,these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors,representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.
基金This work was supported by the National Natural Science Foundation of China (No. 20271011)
文摘A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （tris（hydroxymethyl）aminomethane） and H2O in the molar ratio of 3：1：1：0.5：2.5：1400. Compound 1 crystallizes in the space group P42212 of the tetragonal system with a = b = 21.5009（8）, c = 28.401（2） A, V= 13129.5（12） A^3 Z = 4, Dc = 1.800 g/cm^3, μ（MoKa） = 1.932 mm^-1, λ（MoKa） = 0.71073 A, F（000） = 7063.4, C120H81.20ClCu5N20O38.7V15.35, Mr = 3557.58, the final R = 0.0594 and wR= 0.1320 for 7761 observed reflections （I 〉 2σ（I））. Structure analysis shows that 1 exhibits a 3D channel framework formed by the supramolecular assembly of Cu complexes and polyoxovanadate clusters via intermolecular hydrogen bonding, and the channels contain Cu complexes. Other characterizations by elemental analysis, XPS, IR, XRD and thermal analysis are also described.
基金supported by the National Natural Science Foundation of China (No. 20701012)the Foundation of the Education Ministry of China (No. 207068)the Education Department of Henan Province (No. 2007150003, 2007150011)
文摘A new compound has been synthesized under hydrothermal conditions and characterized by IR, elemental analysis, XPS and single-crystal X-ray diffraction analysis. The title compound [Mn（en）3]2en0.5[HV8VV8IVO38（CI）]·4.5H2O crystallizes in monoclinic, space group C2/c, with a = 17.016（4）, b = 18.858（4）, c = 18.872（4） A, β = 93.667（4）°, V = 6043（2）A3, Z = 4, Dc = 2.242 g/cm3, Mr = 2040.12, F（000） = 4020,μ = 2.895 mm-1, Rint = 0.0921, R = 0.0649 and wR = 0.1325. Single-crystal X-ray structure analysis indicates that the title compound consists of a polyanion [HV8VV8IVO38（CI）]4- cage, two [Mn（en）3]2^2＋ cations, four and a half lattice waters and a half ethylenediamine. In addition, intermolecular O-H...N, O-H...O, N-H...O and C-H...O hydrogen bonds link the molecules together to form a three-dimensional structure.
基金financially supported by National Natural Science Foundation of China(22371032 and 22271023)
文摘The design and synthesis of high-nuclear polyoxometalates(POMs)utilizing secondary building blocks(SBB)is attractive and challenging.Herein,four new high-nuclear polyoxovanadates(POVs),{V_(20)S_(2)In_(42)P_(12)(CO_(2))}(1),{V_(20)Mo_(2)In_(4)P_(12)(C_(2)O_(4))_(2)}(2),{V_(12)P_(6)SPb_(2)}(3)and{V_(12)P_(6)SCd_(2)}(4),were successfully synthesized under solvothermal conditions by incorporating transition metals into POVs.All the structures are constructed from the tetragonal{V_(5)(PhPO_(3))_(4)}SBB,wherein five{VO_(5)}square pyramids are interconnected by edge-sharing modes,and four phenylphosphonic acid ligands further coordinate with vanadium cations.Compounds 1 and 2 have similar structures in which two{V_(10)(PhPO_(3))_(6)(SO_(4))In_(2)}or{V_(10)(PhPO_(3))_(6)(MoO_(4))In_(2)}clusters are bridged by formate or oxalate ligands.While compounds 3 and 4 are constructed from{V_(12)(PhPO_(3))_(6)(SO_(4))}cluster doped with transition metals Pb or Cd.Notably,compound 4 demonstrated efficient catalytic activity for sulfide oxidation.
基金financially supported by the Guangdong Basic and Applied Basic Research Foundation(No.2025A1515010370)Science and Technology Innovation Program of Hunan Province(No.2022RC1115).
文摘Precise control over metal-organic polyhedra(MOPs)architectures via metal and organic linker engineering presents a critical challenge for advancing functional porous materials with specific properties.The rational design of organic linkers and secondary building units(SBUs)with programmable configurational features facilitates the assembly of novel MOPs,wherein structural complexity is enhanced through the integration of low-symmetry linkers and expandable SBUs.Herein,a series of polyoxovanadatebased metal-organic polyhedra(VMOPs)with modulated structures were systematically engineered through linker desymmetrization and SBU expansion approach.Two types of tritopic triazine(D_(3h))-or imidazole(C_(s)/C_(1))-functionalized carboxylate ligands assemble with 3-connected prototype{V_(6)S}or expansional{V_(6)P}clusters,yielding VMOPs that exhibit structural evolution from T_(d)-symmetric regular tetrahedrons to D_(2d)-symmetric isosceles variants.Expansion of vertex clusters leads to structural fine-tuning of VMOPs,giving rise to diverse ligand conformations.Interestingly,these VMOPs exhibit significant differences during the iodine adsorption in both n-hexane solution and gaseous phases,which can be explained by the comprehensive influence of their cavity volume,the functional groups included,and the stacking arrangement.These findings demonstrate an effective structure-designing strategy via regulation of ligand symmetry and SBU architectural features,providing a powerful approach for the customized synthesis of MOPs with tailored structures and functionalities.
基金supported by the Key Science Research Project of Colleges and Universities in Henan Province(Grant No.23A150006)2023 Henan Province Key Research and Development and Promotion Special(Grant Nos.232102230029 and 2211111520600)+2 种基金National Discipline Innovation and Intelligence Introduction Base of Higher Education(Grant No.D23015)the Innovation and Entrepreneurship Training Program for College Students in Henan Province(Grant No.202210481006)Special Project of Nanyang Normal University(Grant Nos.2019ZX009 and 2023QN011).
文摘A new polyoxovanadate-based framework material[Cu(en)_(2)]_(4)V_(18)O_(42)(H_(2)O)·6H_(2)O(1)was designed and synthesized by hydrothermal reaction of NaVO_(3),Cu(NO_(3))_(2)·6H_(2)O and 1,2-diaminoethane(en)via carefully adjusting the pH value of the reaction system.The structure of the title compound has been determined by single-crystal X-ray diff raction analysis,thermogravimetric analysis,infrared spectra and elemental analysis.Detail structural analysis demonstrate the three-dimensional(3D)framework structure of compound 1,which was composed of the[V_(18)O_(42)(H_(2)O)]_(8)−({V_(18)O_(42)(H_(2)O)})anions linked by the Cu^(2+)cations.Compound 1 represents the fi rst 3D framework based on{V_(18)O_(42)(H_(2)O)}polyoxoanions and copper complexes.Solar-driven degradation of residual organic pollutants in industrial wastewater is still a major problem for human beings.Photocatalytic experiments reveal that compound 1 possesses of excellent photocatalytic activity for the degradation of methylene blue and rhodamine B.
基金supported by the Natural Science Foundation of Fujian Province(No.2020J01803)Fujian Provincial Key Laboratory of Featured Materials in Biochemical Industry(FJKL_FBCM202004)the Fujian Provincial Key Laboratory of Ecotoxicological Effects and Control of New Pollutants(PY19001)。
文摘A novel polyoxovanadate-based MOFs microsphere,[Ni(phen)V2O7]·H2O(phen=1,10-phenanthroline),constructed from 3-D discrete nano-sheets has been prepared and characterized by XRD,FT-IR,SEM and TEM.Electrochemical properties as supercapacitor of the as-prepared sample,such as CV,EIS,GCD and the cycle life test have also been studied.The as-prepared MOF(V,Ni)showed a high specific capacitance of 178.09 F×g^(-1) at 1 A×g^(-1) as well as good cycling stability and coulombic efficiency.This work proved that the novel MOFs based on polyoxovanadate hybrid material may serve as a promising electrode material for high-performance supercapacitor.
文摘A novel organic-inorganic hybrid polyoxovanadate, [Ni（bpp）2]2（V4O12） （bpp= 1,3-bi-4-pyridylpropane）, was hydrothermally synthesized from a mix.ture of NiCl2＊6H2O, NH4VO3, bpp, EtOH and H2O. The crystal structure consists of ∞^2[Ni（bpp）2]^2＋, two-dimensional networks interpenetrating perpendicularly with each other, and （V4O12）^4-, cyclic tetranuclear clusters linking the ∞^2[Ni（bpp）2]^2＋ networks to form a three-dimensional coordination framework. The crystal belongs to tetragonal space group I41/a with unit cell parameters, a= 2.14705 nm, c= 1.29293 nm. UV-Vis-NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 2.70 eV.
基金supported by the National Natural Science Foundation of China(Nos.92161111,21901037,21901038)Shanghai Pujiang Program(No.19PJ1400200)+1 种基金the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher LearningInternational Cooperation Fund of Science and Technology Commission of Shanghai Municipality(No.21130750100)。
文摘Three novel polyoxovanadate-based metal-organic frameworks(POV-MOFs),[Co_(2)(1,4-dtzb)_(3)]{V_(4)O_(12)}(V-Co-MOF_(1),1,4-dtzb=1,4-di(4H-1,2,4-triazol-4-yl)benzene],[Co_(3)(1,3-dtzb)_(2)][{V_(6)O_(18)}(V-Co-MOF_(2),1,3-dtzb=1,3-di(4H-1,2,4-triazol-4-yl)benzene],[Co_(4)(4,4’-bdtzb)_(2)]{V_(8)O_(24)}(V-Co-MOF_(3),4,4’-bdtzb=4,4’-(1,1’-biphenyl)-4,4’-diylbis(4H-1,2,4-triazole)benzene]were facilely synthesized and structurally characterized.Single-crystal X-ray diffraction analysis indicates that all the POV-MOFs possess open V sites lined on POV clusters of{V_(4)O_(12)}/{V_(6)O_(18)}/{V_(8)O_(24)}that uniformly distribute on the robust three-dimensional frameworks.This unique structural feature allows them to show high performance for sulfidesulfoxide transformation when performing the reaction in MeOH at 50℃ for 45 min using H_(2)O_(2) as green oxidant.Notably,V-Co-MOF1 exhibited the highest catalytic efficiency,with a conversion>99% and selectivity up to 97% for a series of sulfide substrates.Control reaction demonstrated the catalytically active centers are the open V sites while the MOF skeleton constructed from Co^(2+)and ligands also contributes to enhance the conversion and selectivity via synergistic effect.Furthermore,V-Co-MOF1 can be used as a stable heterogeneous catalyst,and both the structural integrity and catalytic performance were well reserved after five cycles,demonstrating their great potential for advanced catalytic oxidation.
基金supported by the National Natural Science Foundation of China(No.51871113)Natural Science Foundation of Jiangsu Province(No.BK20200047).
文摘Aqueous zinc-ion batteries(ZIBs)are attaining increasing attention for their high safety and low cost.Despite significant progresses in realizing high-performance cathode material for ZIBs,simultaneously endowing them with high capacity and fast-charging capability,the long-term cycling stability remains a major unsolved challenge.In this work,a polyoxovanadate cluster of(NH_(4))_(8)[V_(19)O_(41)(OH)_(9)]·11H_(2)O(NOV)is defined as a cathode material for ZIBs that contains mixed-valence vanadium sites(V^(4+)and V^(5+)).A maximum of 26 electrons can be accommodated in one[V_(19)O_(41)(OH)_(9)]^(8-){V_(19)O_(50)}cluster,contributing to the high theoretical specific capacity of 328 mA·h·g^(-1).The Ti_(3)C_(2)T_(x) MXene nanosheets are incorporated into NOV with the help of ionic liquid(IL)linkers to restrain the dissolution of vanadium species and facilitate electron transport across the electrode.The interfacial bonding,anion exchange,and electrostatic interactions among NOV and MXene are provided by IL liquid.The nanohybrid of NOV-IL-MXene endows excellent contact between MXene and NOV,thereby enhanced charge transfer is observed at interface.Subsequently,the as-synthesized NOV-IL-MXene cathodes exhibit high discharge capacity of 413 mA·h·g^(-1) at 0.2 A·g^(-1) even at high mass loading of 5.2 mg·cm^(-2),remarkable rate performance of 182 mA·h·g^(-1) at 10 A·g^(-1),and impressive cycling stability of 94%capacity retention after 2000 cycles.This work opens up new opportunities to develop advanced polyoxovanadate hybrid cathodes for low-cost and high-performance aqueous ZIBs.
基金supported by the National Natural Science Foundation of China(Nos.92161111,21901037,21901038,21871042)Shanghai Pujiang Program(No.19PJ1400200)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning and International Cooperation Fund of Science and Technology Commission of Shanghai Municipality(No.21130750100)。
文摘Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials.Herein we report the synthesis of sulfonate-functionalized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node.MOPs 1 and 2 exhibit octahedral cage configuration constructed from{V_(5)O_(9)Cl}vertex and 5-sulfoisophthalate linker.Owing to the ordered packing of octahedral cages along three axes,3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2.Coupled with the proton-conductive{V_(5)O_(9)Cl}vertexs as well as protonated counterions,an extensive H-bonded network is therefore generated for facile proton transfer.2 exhibits high proton conductivity of 3.02×10^(-2)S cm^(-1)at 65℃under 90%RH,recording the highest value for MOPs pellet sample.This value is enhanced~1order of magnitude compared with that of carboxylate-functionalized analogue 3,clearly illustrating the advantage of combining linker and metal cluster node for enhanced proton conduction.This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.
基金supported by the Natural Science Foundation of Hunan Province(No.2024JJ5419)the Hunan Provincial Key Research and Development Plan Project in 2024(No.2024JK2074)+1 种基金the Natural Science Foundation of Changsha(No.2023-197)the Open project of the Key Laboratory of digital flavor research of Hunan China Tobacco Industry Co.,Ltd(No.202143000834024).
文摘Multifunctional compatible stealth materials have emerged as the focal point of contemporary protection technology research and vanadium-based nanomaterials play a pivotal role in the development of advanced stealth materials.Here,a compatible stealth aerogel is successfully synthesized by employing mixed-valence decavanadate as the vanadium oxide(VO_(x))molecular model.Ultralight{V^(Ⅳ)VV_(9)}/MXene aerogel(0.0429 g cm^(-3))exhibits exceptional radar stealth performance with a minimal reflection loss(RL_(min))of−57.74 dB(99.9998%EMW absorption)and a significantly superior radar cross section reduction value of 26.77 dB m2.The aerogel’s exceptional properties,including a low infrared(IR)emissivity(0.479)and a low thermal conductivity of(32.30 mW m^(-1)K^(-1)),are crucial for enabling compatibility with IR and thermal stealth technologies.The presence of a mixed-valence polyoxovanadate cluster leads to an increase in the Schottky barrier and enhances magnetic properties,consequently boosting interfacial polarization and contributing to magnetic losses during electromagnetic wave(EMW)absorption.Consequently,altering the number of valence electrons significantly enhances the compatible stealth capabilities.These findings contribute significantly to our comprehension of how microstructure impacts EMW absorption processes and provide a basis for further research into the development of VO_(x)-based compatible stealth materials.
基金financial support by Natural Science Foundation of Science and Technology Department of Jilin Province(20210101131JC).
文摘Polyoxovanadates(POVs)are widely used in various fields,making it crucial to understand the electronic properties for their optimal applications.In this study,the electronic structures of fully-oxidized vanadate anions[V_(n)O_(m)]^(3-/4-)(n=1–5,m=4,7,9,12,14),including[VO_(4)]^(3-),[V_(2)O_(7)]^(4-),[V_(3)O_(9)]^(3-),[V_(4)O_(12)]^(4-),and[V_(5)O_(14)]^(3-),were investigated using density functional theory(DFT)calculations.A comprehensive analysis was conducted on the bond lengths,Wiberg bond index(WBI),bond critical points(BCPs),and covalent composition of these vanadates.The interaction between V―O_(t)and V―O_(b)in studied[V_(n)O_(m)]^(3-/4-)can be viewed as the combination of covalent bond and ionic bond.With an increase in the number of vanadium atoms,the V―O bond lengths decrease,while the covalent composition of V―O bonds increase.In addition,the covalent components of V―O_(t)are larger than those of corresponding V―O_(b).The analysis on charge density indicates that the charge density of cluster decreases as the size of the clusters increases,resulting in a corresponding increase in stability.This study enhances the understanding of the electronic properties of POVs,and the trends indentified are expected to provide valuable information for applications of POVs.
基金Supported by the Opening Project of Key Laboratory of Comprehensive Utilization of Advantage Plants Resources in Hunan South(XNZW14C08)the NSF of Hunan Province(2015JJ2072)+2 种基金the Construct Program of the Key Discipline in Hunan Provincethe Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincethe Project for Undergraduate Research Study and Innovative Experiment of Hunan Provincial(2016-283)
文摘The reactions of the four-coordinated macrocyclic copper complex [CuL]（ClO4）2（L = 1,4,8,11-tetraazacyclotetradecane） with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O（1）, [CuL]3[V（10）O（28）]·8H2O（2） and [Cu L]3[V6O（18）]·8H2O（3）. Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O（18）]6- ring, [V（10）O（28）]6- cluster, and [V（12）O（35）]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2＋ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O（18）]^6- rings in 1 and [V（12）O（35）]^10- rings in 3 into three-dimensional frameworks, respectively.
文摘Compound [V_ 16 O_ 38 (Cl)][Cu(enMe)_2]_ 3.5 ·2H_2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction,elemental analysis,IR,EPR and TGA analysis. The X-ray crystallography shows that compound 1 contains a new {V_ 16 O_ 38 } cluster shell,which is connected by [Cu(enMe)_2] 2+ coordination fragments into a 3-D framework. The compound crystallized in a monoclinic system with space group P2(1)/n,M =2235.82,a =1.26076(3) nm,b =2.55802(6) nm,c =2.14742(4) nm,β =90.7380(10)°, V =6.9250(3) nm 3,Z =4,F (000)=4418,D _c=2.145 g·cm -3 , μ =3.227 mm -1 ,( Δ/σ )=0.000,S =1.066.
