The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
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 tetranuclear square compound (H3O)[Sm2Co2(CDTA)2(DMF)2 (μ4-O) (H2O)6]ClO4 was synthesized through the assembly reaction of Co2+ , Sm3+ and trans-1,2-cclohexylenedinitrilotetraacetic acid (H4CDTA) ...A new tetranuclear square compound (H3O)[Sm2Co2(CDTA)2(DMF)2 (μ4-O) (H2O)6]ClO4 was synthesized through the assembly reaction of Co2+ , Sm3+ and trans-1,2-cclohexylenedinitrilotetraacetic acid (H4CDTA) in aqueous solution. X-ray crystal structural analysis shows that the compound belongs to the monoclinic C2/c space group, with a=27.213(2), b=10.5574(9), c=19.4923(17),β=98.799(1)°, V=5534.1(8)3 , C34H65ClCo2N6O30Sm2 , Mr=1491.93, Dc=1.791g/cm-3 , F(000)=2984,=2.820 mm-1 and Z=4. In the compound, Co2+ is 7-coordianted while Sm3+ is 9-coordinated. With the help of a central O2- and 8 carboxylate oxygen atoms, two Co2+ and two Sm3+ ions are linked into a square with the side length of 3.45 . Magnetic property was investigated.展开更多
The synthesis of heterometallic aluminum-based materials is challenging yet attractive,due to their potential applications in optics,catalysis,magnetism and semiconductor device.We have now successfully synthesized tw...The synthesis of heterometallic aluminum-based materials is challenging yet attractive,due to their potential applications in optics,catalysis,magnetism and semiconductor device.We have now successfully synthesized two Al,Niz heterometallic clusters bearing different peripheral alkoxide ligands through a heterometal substitution strategy.展开更多
2-(2,3-Dihydroxpropyliminomethyl)6-methoxyphenol(H3L), trimethylacetic acid(Hpiv), Gd(NO3)3·6 H2O and Co(NO3)2·6 H2O were reacted in Me OH to obtain a heterometallic tetranuclear cluster [Gd2Co2(L)2(μ3-OH)2...2-(2,3-Dihydroxpropyliminomethyl)6-methoxyphenol(H3L), trimethylacetic acid(Hpiv), Gd(NO3)3·6 H2O and Co(NO3)2·6 H2O were reacted in Me OH to obtain a heterometallic tetranuclear cluster [Gd2Co2(L)2(μ3-OH)2(piv)6]·2 Hpiv·2 CH3OH(1). X-ray crystallographic analysis reveals that compound 1 was found to be a butterfly heterometallic tetranuclear cluster. The crystal(C64H108Co2Gd2N2O28, Mr = 1785.88) belongs to the triclinic crystal system, space group P1 with a =11.9798(6), b = 12.0877(5), c = 15.0367(7) A, α = 67.320(4)°, β = 81.583(4)°, γ = 75.201(4)°, V =1939.62(18) A3, Z = 1, T = 293.15 K, R = 0.048 and w R = 0.144 for 16299 observed reflections with I > 2σ(I). In magnetization study, heterometallic 1 exhibits magnetocaloric effect(MCE) of 14.75 J·kg-1·K-1 at 2 K for ΔH = 5 T, while it does not show non-linear response of the ac-susceptibilities.展开更多
The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1...The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1H/13C--NMR. Theproposal concerning mechanism was discussed herewith and the structure was reportedas well. Crystallographic data: Mr= 563. 85, monoclinicl P21/n(# 14); a= 8. 009(2), b= 17. 600(5), c=12. 003(4) A; β=95. 91(2)°; V= 1683. 0 (9) A3; Z=4;Dc=2. 22 g. cm-3; F(000) = 1048, μ=89. 27 cm-1 ; final R=0. 039 and Rw=0. 049for 2121 observable reflections with (I≥3. cσ(I) ). The crystal structure determinationshows that S atom coordinates to all three metal (W,Fe,Co) atoms in a μ3,-fashion,thetitle cluster core has the tetrahedral skeleton.展开更多
A nonanuclear Cu4^ⅡTi5^Ⅳheterometallic cluster,[Ti5 Cu4 O6(ba)(16)](1,Hba=benzoic acid)was synthesized in one-pot reaction under the solvothermal condition.The metallic skeleton 1 contains a Ti5 core constructed fro...A nonanuclear Cu4^ⅡTi5^Ⅳheterometallic cluster,[Ti5 Cu4 O6(ba)(16)](1,Hba=benzoic acid)was synthesized in one-pot reaction under the solvothermal condition.The metallic skeleton 1 contains a Ti5 core constructed from two vertex-shared Ti3 triangles and four separated Cu atoms outside which are connected together byμ3-O^2- ions.Total 16 ba ligands adoptμ2-η^1:η^1 coordination mode to protect the overall hetero metallic co re.Due to the unique d-d transitions of Cu^Ⅱion,the reflectance spectrum of 1 displays broad and strong absorption towards visible light extending to the near-infrared region.Moreover,1 shows almost purely paramagnetic behavior with the presence of weak antiferromagnetic interactions at low temperatures.展开更多
Catalytic acylation of nitriles with esters in the presence of 10 mol% NdNa8(OtBu)10(OH) is developed.The procedure is suitable for both enolizable and nonenolizable esters and affords β-ketonitriles in moderate to h...Catalytic acylation of nitriles with esters in the presence of 10 mol% NdNa8(OtBu)10(OH) is developed.The procedure is suitable for both enolizable and nonenolizable esters and affords β-ketonitriles in moderate to high yields.The heterometallic alkoxide cluster NdNa8(OtBu)10(OH) is structurally characterized by X-ray diffraction,and a mechanism for the production of β-ketonitriles using the cluster is proposed and verified.展开更多
The reaction of HFe<sub>2</sub>Co(CO)<sub>9</sub>(μ<sub>3</sub>-S)with(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>...The reaction of HFe<sub>2</sub>Co(CO)<sub>9</sub>(μ<sub>3</sub>-S)with(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)Mo(CO)<sub>3</sub>CI has been carried outin refluxing tetrahydrofuran(THF)to give out heterometallic trinuclear clusters(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)MoFeCo-(CO)<sub>8</sub>(μ<sub>3</sub>-S)and(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)<sub>2</sub>Mo<sub>2</sub>Fe(CO)<sub>7</sub>(μ<sub>3</sub>-S)by electrophilic addition-elimination reaction.Howev-er,(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)Fe(CO)<sub>2</sub>Cl reacted with HFe<sub>2</sub>Co(CO)<sub>9</sub>(μ<sub>3</sub>-S)at room temperature to yield a tetranuclearcluster(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)Fe<sub>3</sub>Co(CO)<sub>11</sub>(μ<sub>4</sub>-S).The μ<sub>4</sub>-S cluster could be used as an intermediate in confirmationof the mechanism of the electrophilic addition-elimination reaction.The syntheses,characterizations andX-ray crystal structures of these clusters are reported herein as well as the discussion on the reaction mecha-nism.展开更多
The most effective methodologies for the construction of polynuclear complexes usually take advantage of preorganized building blocks.Herein,we successfully developed a new versatile heterometallic{BiNb_(4)}moiety,whi...The most effective methodologies for the construction of polynuclear complexes usually take advantage of preorganized building blocks.Herein,we successfully developed a new versatile heterometallic{BiNb_(4)}moiety,which can be applied for the assembly of less explored organic-inorganic hybrid polyoxoniobates.Through controlled condensation reactions,three{BiNb_(4)}moieties can be assembled into a pair of isomeric Bi_(3)Nb_(18)clusters at different temperatures;whilst four{BiNb_(4)}moieties can be combined into two unique Bi_(4)Nb_(16)and Bi_(4)Nb_(18)tetramers in different solvents.Interestingly,we have used mass spectrometry to probe the above condensation reactions,which clearly confirmed a stepwise bottom-up assembly process by capturing the presence of bismuth subsalicylate precursors,salicylate coordinated intermediates,Nb incorporated{BiNb_(4)}moieties and the final Bi_(x)Nb_(y)-oxo clusters,respectively.Moreover,the packing modes of the{BiNb_(4)}units induce different solution behaviors,and the{BiNb_(4)}units in Bi4Nb16can be recombined by post-synthetic recrystallization in acetonitrile to produce a new tetramer Bi_(4)Nb_(18)-R.Therefore,this work provides not only a useful{BiNb_(4)}building unit but also the mechanism for their condensation,both of which will promote the future development of metal-oxo clusters.展开更多
Multicomponent binary metal oxide-involved hybrid structures with unique physicochemical properties have received extensive attention due to their fascinating electrochemical performance.Herein,a flexible strategy,whi...Multicomponent binary metal oxide-involved hybrid structures with unique physicochemical properties have received extensive attention due to their fascinating electrochemical performance.Herein,a flexible strategy,which involves the preparation of dual-functional heterometallic Fe_(2)M clusters and their subsequent sintering treatment,is developed to engineer novel 3D hierarchical porous structures assembled with MFe_(2)O_(4)(M=Co,Mn,Ni and Zn)nanoparticles confined within carbon outer shell(denoted as MFe_(2)O_(4)@C HPSs).In this intriguing construction,it can be observed that MFe_(2)O_(4)@C HPSs comprised of carbon coated secondary MFe_(2)O_(4)nanoparticles with an interconnected carbon network.The as-prepared MFe_(2)O_(4)@C HPSs possess combined advantages of high capacity of MFe_(2)O_(4)and high conductivity of carbon.As expected,the MFe_(2)O_(4)@C HPSs offer a high reversible capacity,high cycling stability and superior rate performance.The interconnected conductive carbon shells facilitates fast ion and electron transport and accommodates the mechanical strain.In addition,nanosized MFe_(2)O_(4)particles,which shorten the ion-transport path and provide extra electroactive sites,also improve the reaction kinetics.Moreover,these MFe_(2)O_(4)@C HPSs exhibit good structural integrity during repeated charging and discharging.The research perspective and strategy reported here are highly versatile and shed new light on the synthesis of other advanced electrode for various applications.展开更多
In this work,we report the synthesis and characterization of two novel Ru-containing Zintl clusters:[Sn_(19){Ru(COD)(en)}_(2)]^(4−)and[Sn_(20){Ru(COD)}_(2)]^(6−).The synthesized compounds not only expand the family of...In this work,we report the synthesis and characterization of two novel Ru-containing Zintl clusters:[Sn_(19){Ru(COD)(en)}_(2)]^(4−)and[Sn_(20){Ru(COD)}_(2)]^(6−).The synthesized compounds not only expand the family of Ru-Sn cluster systems but also shed light on the structure of heterometallic complexes in a previously unknown range of tin atoms.The single-crystal X-ray diffraction(XRD)analysis reveals the dimeric nature of the clusters.Two different assembly patterns of the formal[Sn(η^(3)-Sn_(9))]monomer were observed:the dimerization through the vertex fusion process and the direct dimerization through the formation of 2c–2e Sn–Snσbond.For both clusters,the density functional theory calculations reveal the locallyσ-aromatic nature of the[Sn(η^(3)-Sn_(9))]monomer resulting in two independent magnetic shielding cones.We believe that our findings will help the community to further explore the fascinating chemistry of polystannide clusters.展开更多
Single cubane-like clusters, MFe<sub>3</sub>S<sub>4</sub>(R<sub>2</sub>dtc)<sub>5</sub> (M=Mo, R<sub>2</sub>=—(CH<sub>2</sub>)<sub>4&...Single cubane-like clusters, MFe<sub>3</sub>S<sub>4</sub>(R<sub>2</sub>dtc)<sub>5</sub> (M=Mo, R<sub>2</sub>=—(CH<sub>2</sub>)<sub>4</sub>—, Bz<sub>2</sub>; M=W, R<sub>2</sub>=Me<sub>2</sub>, —(CH<sub>2</sub>)4—; dtc=dialkyldithiocarbamate) were synthesized by assembly reaction of (NH<sub>4</sub>)<sub>2</sub>MS<sub>4</sub> (M=Mo, W), FeCl<sub>2</sub> with R<sub>2</sub>dtcNa (or NH<sub>4</sub>) in DMF. The structure, IR, EPR and cyclic voltammogram are described and discussed. MoFe<sub>3</sub>S<sub>4</sub>(C<sub>4</sub>H<sub>8</sub>dtc)<sub>5</sub> was also obtained from the conversion of linear cluster Fe(DMF)<sub>6</sub>[(FeCl<sub>2</sub>)<sub>2</sub>MoS<sub>4</sub>] in the presence of C<sub>4</sub>H<sub>8</sub>dtc NH<sub>4</sub>. Both clusters MoFe<sub>3</sub>S<sub>4</sub>(C<sub>4</sub>H<sub>8</sub>dtc)<sub>4</sub>·2C<sub>2</sub>H<sub>5</sub>CN and WFe<sub>3</sub>S<sub>4</sub>(C<sub>4</sub>H<sub>8</sub>dtc)<sub>5</sub>·2DMF crystallize in the monoclinic space group C2/c with a=12.544(2), (Mo-cluster), 12.533(4) (W-cluster); b=20.478(4), 20.121(6); c=19.582(7), 19.659(2);β=102.82(2), 102.96(3)°; and Z=4, 4. Their structures were refined to R=0.057 and 0.064 with use of 2690 and 2179 reflections (ι】3Q(I)), respectively. Many similarities in structure for Mo and W clusters indicate that both Mo and W play a very similar role in the clusters.展开更多
The features of synthetic processes are described on the basis of the studies of the syntheses of MoFe<sub>3</sub>S<sub>4</sub> cubane-like cluster compounds either by self-assembly reactions o...The features of synthetic processes are described on the basis of the studies of the syntheses of MoFe<sub>3</sub>S<sub>4</sub> cubane-like cluster compounds either by self-assembly reactions or by the conversion of linear clusters. The redox properties and the structure of ligands as well as the stoichiometry of reactants have obvious effects upon the core oxidation state and the structure of products. It is indicated that the self-assembly reaction may pass through a combination process oflinear cluster intermediates having structural unit (M,M’=Mo) Fe).展开更多
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.
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 NNSFC (21071025, 91122031)Doctoral Fund of Ministry of Education of China (20100041120021)DUT (893127 and 851004)
文摘A new tetranuclear square compound (H3O)[Sm2Co2(CDTA)2(DMF)2 (μ4-O) (H2O)6]ClO4 was synthesized through the assembly reaction of Co2+ , Sm3+ and trans-1,2-cclohexylenedinitrilotetraacetic acid (H4CDTA) in aqueous solution. X-ray crystal structural analysis shows that the compound belongs to the monoclinic C2/c space group, with a=27.213(2), b=10.5574(9), c=19.4923(17),β=98.799(1)°, V=5534.1(8)3 , C34H65ClCo2N6O30Sm2 , Mr=1491.93, Dc=1.791g/cm-3 , F(000)=2984,=2.820 mm-1 and Z=4. In the compound, Co2+ is 7-coordianted while Sm3+ is 9-coordinated. With the help of a central O2- and 8 carboxylate oxygen atoms, two Co2+ and two Sm3+ ions are linked into a square with the side length of 3.45 . Magnetic property was investigated.
基金This work is supported by the National Natural Science Foundation of China(92061104,21935010 and 21973096)the Natural Science Foundation of Fujian Province(2021J06035)the Youth Innovation Promotion Association CAS(Y2018081).
文摘The synthesis of heterometallic aluminum-based materials is challenging yet attractive,due to their potential applications in optics,catalysis,magnetism and semiconductor device.We have now successfully synthesized two Al,Niz heterometallic clusters bearing different peripheral alkoxide ligands through a heterometal substitution strategy.
基金supported by the National Natural Science Foundation of China(No.21771043,51572050 and 21601038)Guangxi Natural Science Foundation(No.2015GXNSFDA139007 and 2016GXNSFAA380085)Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials(EMFM20162107)
文摘2-(2,3-Dihydroxpropyliminomethyl)6-methoxyphenol(H3L), trimethylacetic acid(Hpiv), Gd(NO3)3·6 H2O and Co(NO3)2·6 H2O were reacted in Me OH to obtain a heterometallic tetranuclear cluster [Gd2Co2(L)2(μ3-OH)2(piv)6]·2 Hpiv·2 CH3OH(1). X-ray crystallographic analysis reveals that compound 1 was found to be a butterfly heterometallic tetranuclear cluster. The crystal(C64H108Co2Gd2N2O28, Mr = 1785.88) belongs to the triclinic crystal system, space group P1 with a =11.9798(6), b = 12.0877(5), c = 15.0367(7) A, α = 67.320(4)°, β = 81.583(4)°, γ = 75.201(4)°, V =1939.62(18) A3, Z = 1, T = 293.15 K, R = 0.048 and w R = 0.144 for 16299 observed reflections with I > 2σ(I). In magnetization study, heterometallic 1 exhibits magnetocaloric effect(MCE) of 14.75 J·kg-1·K-1 at 2 K for ΔH = 5 T, while it does not show non-linear response of the ac-susceptibilities.
文摘The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1H/13C--NMR. Theproposal concerning mechanism was discussed herewith and the structure was reportedas well. Crystallographic data: Mr= 563. 85, monoclinicl P21/n(# 14); a= 8. 009(2), b= 17. 600(5), c=12. 003(4) A; β=95. 91(2)°; V= 1683. 0 (9) A3; Z=4;Dc=2. 22 g. cm-3; F(000) = 1048, μ=89. 27 cm-1 ; final R=0. 039 and Rw=0. 049for 2121 observable reflections with (I≥3. cσ(I) ). The crystal structure determinationshows that S atom coordinates to all three metal (W,Fe,Co) atoms in a μ3,-fashion,thetitle cluster core has the tetrahedral skeleton.
基金financially supported by the National Natural Science Foundation of China(Nos.21822107,21571115)the Natural Science Foundation of Shandong Province(Nos.BS2014CL042,ZR2017ZF003,JQ201803,ZR2017MB061)+6 种基金the Taishan Scholar Project of Shandong Province of Chinathe Qilu Youth Scholar Funding of Shandong Universitythe Fundamental Research Funds of Shandong University(No.104.205.2.5)the Slovenian Research Agency(No.P2-0348)Bilateral Project PR China-Slovenian(No.BI-CN/17-18-004)the State Key Laboratory of Pollution Control and Resource Reuse Foundation(No.PCRRF18019)financial support from the government of Shandong Province for visiting abroad。
文摘A nonanuclear Cu4^ⅡTi5^Ⅳheterometallic cluster,[Ti5 Cu4 O6(ba)(16)](1,Hba=benzoic acid)was synthesized in one-pot reaction under the solvothermal condition.The metallic skeleton 1 contains a Ti5 core constructed from two vertex-shared Ti3 triangles and four separated Cu atoms outside which are connected together byμ3-O^2- ions.Total 16 ba ligands adoptμ2-η^1:η^1 coordination mode to protect the overall hetero metallic co re.Due to the unique d-d transitions of Cu^Ⅱion,the reflectance spectrum of 1 displays broad and strong absorption towards visible light extending to the near-infrared region.Moreover,1 shows almost purely paramagnetic behavior with the presence of weak antiferromagnetic interactions at low temperatures.
基金supported by the National Natural Science Foundation of China (20872106 and 20972107)
文摘Catalytic acylation of nitriles with esters in the presence of 10 mol% NdNa8(OtBu)10(OH) is developed.The procedure is suitable for both enolizable and nonenolizable esters and affords β-ketonitriles in moderate to high yields.The heterometallic alkoxide cluster NdNa8(OtBu)10(OH) is structurally characterized by X-ray diffraction,and a mechanism for the production of β-ketonitriles using the cluster is proposed and verified.
文摘The reaction of HFe<sub>2</sub>Co(CO)<sub>9</sub>(μ<sub>3</sub>-S)with(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)Mo(CO)<sub>3</sub>CI has been carried outin refluxing tetrahydrofuran(THF)to give out heterometallic trinuclear clusters(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)MoFeCo-(CO)<sub>8</sub>(μ<sub>3</sub>-S)and(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)<sub>2</sub>Mo<sub>2</sub>Fe(CO)<sub>7</sub>(μ<sub>3</sub>-S)by electrophilic addition-elimination reaction.Howev-er,(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)Fe(CO)<sub>2</sub>Cl reacted with HFe<sub>2</sub>Co(CO)<sub>9</sub>(μ<sub>3</sub>-S)at room temperature to yield a tetranuclearcluster(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>CH<sub>3</sub>)Fe<sub>3</sub>Co(CO)<sub>11</sub>(μ<sub>4</sub>-S).The μ<sub>4</sub>-S cluster could be used as an intermediate in confirmationof the mechanism of the electrophilic addition-elimination reaction.The syntheses,characterizations andX-ray crystal structures of these clusters are reported herein as well as the discussion on the reaction mecha-nism.
基金supported by the National Natural Science Foundation of China(21922111 and 91961108)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)。
文摘The most effective methodologies for the construction of polynuclear complexes usually take advantage of preorganized building blocks.Herein,we successfully developed a new versatile heterometallic{BiNb_(4)}moiety,which can be applied for the assembly of less explored organic-inorganic hybrid polyoxoniobates.Through controlled condensation reactions,three{BiNb_(4)}moieties can be assembled into a pair of isomeric Bi_(3)Nb_(18)clusters at different temperatures;whilst four{BiNb_(4)}moieties can be combined into two unique Bi_(4)Nb_(16)and Bi_(4)Nb_(18)tetramers in different solvents.Interestingly,we have used mass spectrometry to probe the above condensation reactions,which clearly confirmed a stepwise bottom-up assembly process by capturing the presence of bismuth subsalicylate precursors,salicylate coordinated intermediates,Nb incorporated{BiNb_(4)}moieties and the final Bi_(x)Nb_(y)-oxo clusters,respectively.Moreover,the packing modes of the{BiNb_(4)}units induce different solution behaviors,and the{BiNb_(4)}units in Bi4Nb16can be recombined by post-synthetic recrystallization in acetonitrile to produce a new tetramer Bi_(4)Nb_(18)-R.Therefore,this work provides not only a useful{BiNb_(4)}building unit but also the mechanism for their condensation,both of which will promote the future development of metal-oxo clusters.
基金the financial support provided by the National Natural Science Foundation of China(No.21871164)the Taishan Scholar Project Foundation of Shandong Province(No.ts20190908)+2 种基金the Natural Science Foundation of Shandong Province(No.ZR2019MB024)the China Postdoctoral Science Foundation(No.2018M632666)the Special Fund for Postdoctoral Innovation Program of Shandong Province(No.201901003)。
文摘Multicomponent binary metal oxide-involved hybrid structures with unique physicochemical properties have received extensive attention due to their fascinating electrochemical performance.Herein,a flexible strategy,which involves the preparation of dual-functional heterometallic Fe_(2)M clusters and their subsequent sintering treatment,is developed to engineer novel 3D hierarchical porous structures assembled with MFe_(2)O_(4)(M=Co,Mn,Ni and Zn)nanoparticles confined within carbon outer shell(denoted as MFe_(2)O_(4)@C HPSs).In this intriguing construction,it can be observed that MFe_(2)O_(4)@C HPSs comprised of carbon coated secondary MFe_(2)O_(4)nanoparticles with an interconnected carbon network.The as-prepared MFe_(2)O_(4)@C HPSs possess combined advantages of high capacity of MFe_(2)O_(4)and high conductivity of carbon.As expected,the MFe_(2)O_(4)@C HPSs offer a high reversible capacity,high cycling stability and superior rate performance.The interconnected conductive carbon shells facilitates fast ion and electron transport and accommodates the mechanical strain.In addition,nanosized MFe_(2)O_(4)particles,which shorten the ion-transport path and provide extra electroactive sites,also improve the reaction kinetics.Moreover,these MFe_(2)O_(4)@C HPSs exhibit good structural integrity during repeated charging and discharging.The research perspective and strategy reported here are highly versatile and shed new light on the synthesis of other advanced electrode for various applications.
基金supported by the National Natural Science Foundation of China(Nos.92161102 and 21971118)the Natural Science Foundation of Tianjin City(Nos.20JCYBJC01560 and B2021202077)+2 种基金Z.M.S.A.I.B.acknowledges financial support from the R.Gaurth Hansen Professorship fundThe support and resources from the Centre for High Performance Computing at the University of Utah are gratefully acknowledged.A.M.C.acknowledges financial support from FONDECYT 1180683We also thank the valuable discussion from Professor Slavi C.Sevov(Department of Chemistry and Biochemistry,University of Notre Dame).
文摘In this work,we report the synthesis and characterization of two novel Ru-containing Zintl clusters:[Sn_(19){Ru(COD)(en)}_(2)]^(4−)and[Sn_(20){Ru(COD)}_(2)]^(6−).The synthesized compounds not only expand the family of Ru-Sn cluster systems but also shed light on the structure of heterometallic complexes in a previously unknown range of tin atoms.The single-crystal X-ray diffraction(XRD)analysis reveals the dimeric nature of the clusters.Two different assembly patterns of the formal[Sn(η^(3)-Sn_(9))]monomer were observed:the dimerization through the vertex fusion process and the direct dimerization through the formation of 2c–2e Sn–Snσbond.For both clusters,the density functional theory calculations reveal the locallyσ-aromatic nature of the[Sn(η^(3)-Sn_(9))]monomer resulting in two independent magnetic shielding cones.We believe that our findings will help the community to further explore the fascinating chemistry of polystannide clusters.
基金Project supported by the National Natural Science Foundation of China and the Science Foundation of Academia Sinica.
文摘Single cubane-like clusters, MFe<sub>3</sub>S<sub>4</sub>(R<sub>2</sub>dtc)<sub>5</sub> (M=Mo, R<sub>2</sub>=—(CH<sub>2</sub>)<sub>4</sub>—, Bz<sub>2</sub>; M=W, R<sub>2</sub>=Me<sub>2</sub>, —(CH<sub>2</sub>)4—; dtc=dialkyldithiocarbamate) were synthesized by assembly reaction of (NH<sub>4</sub>)<sub>2</sub>MS<sub>4</sub> (M=Mo, W), FeCl<sub>2</sub> with R<sub>2</sub>dtcNa (or NH<sub>4</sub>) in DMF. The structure, IR, EPR and cyclic voltammogram are described and discussed. MoFe<sub>3</sub>S<sub>4</sub>(C<sub>4</sub>H<sub>8</sub>dtc)<sub>5</sub> was also obtained from the conversion of linear cluster Fe(DMF)<sub>6</sub>[(FeCl<sub>2</sub>)<sub>2</sub>MoS<sub>4</sub>] in the presence of C<sub>4</sub>H<sub>8</sub>dtc NH<sub>4</sub>. Both clusters MoFe<sub>3</sub>S<sub>4</sub>(C<sub>4</sub>H<sub>8</sub>dtc)<sub>4</sub>·2C<sub>2</sub>H<sub>5</sub>CN and WFe<sub>3</sub>S<sub>4</sub>(C<sub>4</sub>H<sub>8</sub>dtc)<sub>5</sub>·2DMF crystallize in the monoclinic space group C2/c with a=12.544(2), (Mo-cluster), 12.533(4) (W-cluster); b=20.478(4), 20.121(6); c=19.582(7), 19.659(2);β=102.82(2), 102.96(3)°; and Z=4, 4. Their structures were refined to R=0.057 and 0.064 with use of 2690 and 2179 reflections (ι】3Q(I)), respectively. Many similarities in structure for Mo and W clusters indicate that both Mo and W play a very similar role in the clusters.
文摘The features of synthetic processes are described on the basis of the studies of the syntheses of MoFe<sub>3</sub>S<sub>4</sub> cubane-like cluster compounds either by self-assembly reactions or by the conversion of linear clusters. The redox properties and the structure of ligands as well as the stoichiometry of reactants have obvious effects upon the core oxidation state and the structure of products. It is indicated that the self-assembly reaction may pass through a combination process oflinear cluster intermediates having structural unit (M,M’=Mo) Fe).