Charge and spin orders are intimately related to superconductivity in copper oxide superconductors.Elucidation of the competing orders in various nickel oxide compounds is crucial,given the fact that superconductivity...Charge and spin orders are intimately related to superconductivity in copper oxide superconductors.Elucidation of the competing orders in various nickel oxide compounds is crucial,given the fact that superconductivity has been discovered in Nd_(0.8)Sr_(0.2)NiO_(2)films.Herein,we report structural,electronic transport,magnetic,and thermodynamic characterizations of single crystals of La_(3)Ni_(2)O_(7)and La_(3)Ni_(2)O_(6).La_(3)Ni_(2)O_(7)is metallic with mixed Ni^(2+)and Ni^(3+)valent states.Resistivity measurements yield two transition-like kinks at~110 and 153 K.The kink at 153 K is further revealed from magnetization and specific heat measurements,indicative of the formation of charge and spin density waves.La_(3)Ni_(2)O_(6)single crystals obtained from the topochemical reduction of La_(3)Ni_(2)O_(7)are insulating and show an anomaly at~176 K on magnetic susceptibility.The transition-like behaviors of La_(3)Ni_(2)O_(7)and La_(3)Ni_(2)O_(6)are analogous to those observed in La_(4)Ni_(3)O_(10) and La_(4)Ni_(3)O_(8),suggesting that charge and spin density waves are a common feature in the ternary La-Ni-O system with mixed-valent states of nickel.展开更多
Lithium-oxygen batteries(LOBs)have extensive applications because of their ultra-high energy densities.However,the practical application of LOBs is limited by several factors,such as a high overpotential,poor cycle st...Lithium-oxygen batteries(LOBs)have extensive applications because of their ultra-high energy densities.However,the practical application of LOBs is limited by several factors,such as a high overpotential,poor cycle stability,and limited rate capacity.In this paper,we describe the successful uniform loading of Mn_(3)O_(4) nanoparticles onto multi-walled carbon nanotubes(Mn_(3)O_(4)@CNT).CNTs form a conductive network and expose numerous catalytically active sites,and the one-dimensional porous structure provides a convenient channel for the transmission of Li+and O2 in LOBs.The electronic conductivity and electrocatalytic activity of Mn_(3)O_(4)@CNT are significantly better than those of MnO@CNT because of the inherent driving force facilitating charge transfer between different valence metal ions.Therefore,the Mn_(3)O_(4)@CNT cathode obtains a low overpotential(0.76 V at a limited capacity of 1000 mAh g^(-1)),high initial discharge capacity(16895 mAh g^(-1) at 200 mA g^(-1)),and long cycle life(97 cycles at 200 mA g^(-1)).This study provides evidence that transition metal oxides with mixed-valence states are suitable for application as efficient cathodes for LOBs.展开更多
A novel inorganic-organic hybrid compound, {[Co（dien）]4[0aO4）MoV8（wV10.56MoV10.44）4- O33（OH）3]}＇nH20 （1, n = 1, dien = diethylenetriamine）, has been synthesized hydrothermally and characterized by single-cry...A novel inorganic-organic hybrid compound, {[Co（dien）]4[0aO4）MoV8（wV10.56MoV10.44）4- O33（OH）3]}＇nH20 （1, n = 1, dien = diethylenetriamine）, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system with a = 11.927（2）, b = 13.328（3）, c = 19.306（4）A, a = 93.76（3）, β = 94.14（3）, γ = 109.99（3）°, V= 2863.2（12） A3, space group P1 and Z = 2 at 173 K. The final full-matrix least-squares refinement converged to R = 0.049 for 9621 observed reflections with 1 〉 2σ（I） and wR = 0.139 for all data （9871） and S = 1.073. Crystal structure analysis shows that 1 contains a kind of the first reported mixed-valence and molybdenum-tungsten mixed-distributed e-Keggin structural polyanion capped by four Co（dien） fragments with the main group element P occupying the center site. These results were further confirmed by energy-dispersive X-ray spectroscopy （EDS）, X-ray powder diffraction （XRD）, Fourier transform infrared spectroscopy （FTIR）, Raman spectroscopy, Thermogravimetry （TG） and X-ray photoelectron spectroscopy （XPS） analyses.展开更多
Mixed-valence is an effective way to achieve high electrochemical performance of anodes for supercapacitor.However,inordinate mixed valence with more structural defects leads to structural instability.The development ...Mixed-valence is an effective way to achieve high electrochemical performance of anodes for supercapacitor.However,inordinate mixed valence with more structural defects leads to structural instability.The development of mixed valence electrodes that can maintain a stable structure during the defect formation process is the key to resolving this problem.Cu_(2-x)Se with mixed-valence is a potential candidate,the stable monoclinic structure of Cu2Se can be transformed into another stable cubic structure(x>0.15).Herein,Cu_(1.85)Se anode with mixed valence reveals the ultrahigh specific capacity of 247.8 mA·h/g at 2 A/g.Furthermore,the introduction of multi-walled carbon nanotubes(MWCNTs)into Cu1.85Se further improves the specific capacity(435 mA·h/g at 2 A/g).XRD shows that the introduction of MWCNTs can improve the reversibility via chemical interactions and accelerate the electron transfer in the Cu1.85Se/MWCNTs.Notably,the assembled symmetric supercapacitor(SC)device expresses a high energy density of 41.4 W·h/kg,and the capacity remains 83%even after 8000 charge/discharge cycles.This research demonstrates the great potential of developing high specific capacity anode materials for superior performance supercapacitor.展开更多
Copper (Ⅱ) α-methacrylate reacts with triphenylphosphine to form whxed-valence copper (Ⅰ,Ⅱ) complex Cu4(CH2=C(CH3)COO)6(PPh3)4(CH3OH）2 in methanol solution. The crystal and molecular structure of the complex has ...Copper (Ⅱ) α-methacrylate reacts with triphenylphosphine to form whxed-valence copper (Ⅰ,Ⅱ) complex Cu4(CH2=C(CH3)COO)6(PPh3)4(CH3OH）2 in methanol solution. The crystal and molecular structure of the complex has been detendned by single crystal X-ray structural analysis. This material forms pale green crystals with triclinic symmetry, space group Pi, a=1 .3567(2) nm, b=1.3946 (3) nm, c=1.4569 (3) nm, α=66.069 (14)0, β=84.234 (14)0 γ=69.975 (13)0,R=0.0536.展开更多
Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is...Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is vital to improve the kinetics of ammonia synthesis and obtain a less energy-intensive process.Herein,carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) was prepared and applied as an electrocatalyst for high-efficiency NRR.A dramatic faradaic efficiency(FE)of 36.93%and an NH_(3) production rate of 13.1μg h^(-1) mg_(cat)^(-1) were obtained at-0.3 V versus RHE,superior to nearly all Fe-based catalysts.Experiments and DFT calculations revealed that the superior performance was ascribed to the synergistic effect of mixed-valence iron pair,which braked the linear correlations to improve the kinetics of ammonia from collaborative hydrogenation and*NH_(3) separation.This work proves the feasibility of mixedvalence catalysts for nitrogen reduction and thus opening a new avenue towards artificial nitrogenfixation catalysts.展开更多
Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-...Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964（5）, b = 10.2592, c = 10.5822（8） A, V = 933.01（9） A3, Z = 2, C_（30）H_（24）Br_4Cu_3N_（12）O_2P_2, M_r = 985.02, D_c = 1.753 g/cm3, F（000） = 4072 and μ（MoKα） = 0.746 mm^（-1）. The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 〉 2σ（I）. Cu（Ⅰ） is tetrahedrally coordinated and Cu（Ⅱ） center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N-H···O and N-H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.展开更多
A new layered mixed valence vanadium oxide, [CH 3NH 3] 2[(V ⅣO) 2(V ⅤO 4) 2], which contains interlamellar organic cations was prepared under hydrothermal conditions and its single crystal structure was determined. ...A new layered mixed valence vanadium oxide, [CH 3NH 3] 2[(V ⅣO) 2(V ⅤO 4) 2], which contains interlamellar organic cations was prepared under hydrothermal conditions and its single crystal structure was determined. It crystallizes in a triclinic system with space group P 1, a =0 625 59(8) nm, b =0 639 84(9) nm, c =0 747 19(10) nm, α =78 718(2)°, β =80 099(2)°, γ =77 100(2). The compound contains mixed valence V 4+ /V 5+ vanadium oxide layers constructed from VO 4 tetrahedra, pairs of edge sharing VO 5 square pyramid and methylamine with protonated organic amines occupying the interlayer space.展开更多
The mixed-valence isopolyanion Mo6O193- was investigated by means of cyclic voltammographic, in-situ FTIR and UV-Visible-Near-IR spectro-electrochemicalmethods in aprotic media. The experimental results indicate that ...The mixed-valence isopolyanion Mo6O193- was investigated by means of cyclic voltammographic, in-situ FTIR and UV-Visible-Near-IR spectro-electrochemicalmethods in aprotic media. The experimental results indicate that the Mo6O193-was formed whereafter Mo6O193- was reduced, (E0' = - 0. 690 V, n = 1 ). The characteristic absorptions of Mo6O193- are 500 nm, 900 nm and 1100 nm in UV-VisibleNear-IR spectrum and 940 cm-1 in IR spectrum.展开更多
A series of {2Fe3S} complexes bearing phosphino thioether chelating ligand were synthesized on the basis of Fe2（Me2pdt）（1,2-Cy2PC6H4SMe）（CO）4 （Me2pdt= Me2C（CH2S ）2, 1）. The disubstituted Fe（1）Fe（1） compo...A series of {2Fe3S} complexes bearing phosphino thioether chelating ligand were synthesized on the basis of Fe2（Me2pdt）（1,2-Cy2PC6H4SMe）（CO）4 （Me2pdt= Me2C（CH2S ）2, 1）. The disubstituted Fe（1）Fe（1） compound 1 exhibits a reversible one-electron redox even for [Fe（Ⅰ）Fe（Ⅱ）]＋/0 couple. Based on the oxidation of I to [1]＋, the tri-substituted [Fe（Ⅰ）Fe（Ⅱ）]＋ cationic complex [Fe2/Me2pdt）/1,2-Cy2PC6H4SMe） （PPh3）（CO）3]＋ （[2]＋） was synthesized. Reduction of [2]＋ provided the neutral tri-substituted Fe（l）Fe（1） compound 2. The substitution of the CO in I ligand by PPh3 results in an anodic shift of the Fe11Fe＋/Fe1Fe1 couple of470 mV. Most importantly, this substitution also leads to the Fe-Fe bonds in 1 and 2 with large Lewis basicity difference, i.e. △pKaMeCN ～ 10.展开更多
Reaction of [Mo3(CO)7(S,O-C6H4-1,2)3]2- with FeCl2 in MeCN at 60℃ affords a new Mo-Fe-S cluster complex containing MoO3S3 unit and mixed-valeut Mo atoms, [Et4N]2[Mo2Fe-(CO)4(O,S-C6H4-1,2)aCl2] (1). 1 is characterize... Reaction of [Mo3(CO)7(S,O-C6H4-1,2)3]2- with FeCl2 in MeCN at 60℃ affords a new Mo-Fe-S cluster complex containing MoO3S3 unit and mixed-valeut Mo atoms, [Et4N]2[Mo2Fe-(CO)4(O,S-C6H4-1,2)aCl2] (1). 1 is characterized by elemental analysis, IR, Mossbauer spectra, X-ray photoelectron spectra and mass spectra. And the structure of 1 is suggested as the structure which contains a [Mo(S,O-C6H4-1,2)3] unit of which the two of three sulfur atoms link to a Mo(CO)4-moiety and the three oxygen atoms are coordinated to a FeCl2 ligand.展开更多
A mixed-valent hexanuclear complex [Cu^ⅡCu^Ⅰ2（pbi）2Br2]2 （pbi = （2-（2-pyridyl）-benzimidazole） exhibiting a dimeric unit bridged by two Br atoms was synthesized by hydrothermal reaction Interestingly, there ex...A mixed-valent hexanuclear complex [Cu^ⅡCu^Ⅰ2（pbi）2Br2]2 （pbi = （2-（2-pyridyl）-benzimidazole） exhibiting a dimeric unit bridged by two Br atoms was synthesized by hydrothermal reaction Interestingly, there exist intramolecular and intermolecular n^zstacking interactions as well as metalaromatic ring interactions in the title complex. The crystal belongs to the monoclinic system, space group P1, with a = 7.1061（9）, b = 12.1008（13）, c = 14.0711（17） A, α=91.742（8）,β=100.155（9）, γ=90.486（7）°, V = 1190.3（2） A^3, Z = 2, C48H32Br4CucoNt2, Mr = 1477.74, Dc= 2.061 g/cm^3, F（000） = 718, μ（MoKα） = 6.039 mm^-1, the final R = 0.0481 and wR = 0.0974 for 3426 observed reflections （I 〉 2σ（I））.展开更多
A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoc...A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].展开更多
Five polynuclear monovalent and mixed-valence complexes of copper with 2-thiouracil were synthesized. They were characterized by the molar conductivity, electromc spectra, infrared spectroscopy, thermogravimetric and ...Five polynuclear monovalent and mixed-valence complexes of copper with 2-thiouracil were synthesized. They were characterized by the molar conductivity, electromc spectra, infrared spectroscopy, thermogravimetric and magnetic susceptibility measurements. Their coordination properties and tentative structures were discussed.展开更多
The title compound was prepared by solid state reaction of LaCl_3/V inan evacuated silica tube where the silicon came from the reaction tube. The compoundcrystallizes in monoclinic space group C2/m with cell dimension...The title compound was prepared by solid state reaction of LaCl_3/V inan evacuated silica tube where the silicon came from the reaction tube. The compoundcrystallizes in monoclinic space group C2/m with cell dimensions of a=13. 482 (7), b=5. 604(3), c=11. 091(3) A, β=100. 44(3)°, V=824(1) A3, Mr= 1274. 66 , Dc=5. 14 g/cm3, F(000) = 1150, μ- 13. 20 mm-1 and Z=2; final R=0. 061, Rw=0. 054for 1037 observed reflections (Ⅰ>3σ(Ⅰ) ) . It is isostructural with quasi-ZD Pr_4V_5Si_4O_(22)compound with the Ⅴ-Ⅴ distances across the shared VO6 octahedral edges of 2. 802 Aand vanadium ions show mixed-valence(Ⅲ/Ⅳ) with an average value of+ 3. 2.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.12174454,11904414,11904416,and U2130101)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2021B1515120015)+1 种基金the Guangzhou Basic and Applied Basic Research Foundation(Grant No.202201011123)the National Key Research and Development Program of China(Grant Nos.2019YFA0705702,2020YFA0406003,2021YFA1400401,and 2021YFA0718900)。
文摘Charge and spin orders are intimately related to superconductivity in copper oxide superconductors.Elucidation of the competing orders in various nickel oxide compounds is crucial,given the fact that superconductivity has been discovered in Nd_(0.8)Sr_(0.2)NiO_(2)films.Herein,we report structural,electronic transport,magnetic,and thermodynamic characterizations of single crystals of La_(3)Ni_(2)O_(7)and La_(3)Ni_(2)O_(6).La_(3)Ni_(2)O_(7)is metallic with mixed Ni^(2+)and Ni^(3+)valent states.Resistivity measurements yield two transition-like kinks at~110 and 153 K.The kink at 153 K is further revealed from magnetization and specific heat measurements,indicative of the formation of charge and spin density waves.La_(3)Ni_(2)O_(6)single crystals obtained from the topochemical reduction of La_(3)Ni_(2)O_(7)are insulating and show an anomaly at~176 K on magnetic susceptibility.The transition-like behaviors of La_(3)Ni_(2)O_(7)and La_(3)Ni_(2)O_(6)are analogous to those observed in La_(4)Ni_(3)O_(10) and La_(4)Ni_(3)O_(8),suggesting that charge and spin density waves are a common feature in the ternary La-Ni-O system with mixed-valent states of nickel.
基金the Nature Science Foun-dation of Shandong Province(Grant No:ZR2019BEM019)Future Plans of Young Scholars at Shandong University.
文摘Lithium-oxygen batteries(LOBs)have extensive applications because of their ultra-high energy densities.However,the practical application of LOBs is limited by several factors,such as a high overpotential,poor cycle stability,and limited rate capacity.In this paper,we describe the successful uniform loading of Mn_(3)O_(4) nanoparticles onto multi-walled carbon nanotubes(Mn_(3)O_(4)@CNT).CNTs form a conductive network and expose numerous catalytically active sites,and the one-dimensional porous structure provides a convenient channel for the transmission of Li+and O2 in LOBs.The electronic conductivity and electrocatalytic activity of Mn_(3)O_(4)@CNT are significantly better than those of MnO@CNT because of the inherent driving force facilitating charge transfer between different valence metal ions.Therefore,the Mn_(3)O_(4)@CNT cathode obtains a low overpotential(0.76 V at a limited capacity of 1000 mAh g^(-1)),high initial discharge capacity(16895 mAh g^(-1) at 200 mA g^(-1)),and long cycle life(97 cycles at 200 mA g^(-1)).This study provides evidence that transition metal oxides with mixed-valence states are suitable for application as efficient cathodes for LOBs.
基金Foundation of Education Department of Fujian Province(Nos.JA11245 and JB12199)National Natural Science Foundation of China(No.40972035)
文摘A novel inorganic-organic hybrid compound, {[Co（dien）]4[0aO4）MoV8（wV10.56MoV10.44）4- O33（OH）3]}＇nH20 （1, n = 1, dien = diethylenetriamine）, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system with a = 11.927（2）, b = 13.328（3）, c = 19.306（4）A, a = 93.76（3）, β = 94.14（3）, γ = 109.99（3）°, V= 2863.2（12） A3, space group P1 and Z = 2 at 173 K. The final full-matrix least-squares refinement converged to R = 0.049 for 9621 observed reflections with 1 〉 2σ（I） and wR = 0.139 for all data （9871） and S = 1.073. Crystal structure analysis shows that 1 contains a kind of the first reported mixed-valence and molybdenum-tungsten mixed-distributed e-Keggin structural polyanion capped by four Co（dien） fragments with the main group element P occupying the center site. These results were further confirmed by energy-dispersive X-ray spectroscopy （EDS）, X-ray powder diffraction （XRD）, Fourier transform infrared spectroscopy （FTIR）, Raman spectroscopy, Thermogravimetry （TG） and X-ray photoelectron spectroscopy （XPS） analyses.
基金The work is funded by the subproject of the National Key Research and Development Program of China(2017YFC0602102)the Department of Science and Technology of Sichuan Province(2021JDTD0030)+1 种基金the National Natural Science Foundation of China(No.U20A20213,61727818,51874184)the Chengdu Science and Technology Project(2020-GH02-0065-HZ)。
文摘Mixed-valence is an effective way to achieve high electrochemical performance of anodes for supercapacitor.However,inordinate mixed valence with more structural defects leads to structural instability.The development of mixed valence electrodes that can maintain a stable structure during the defect formation process is the key to resolving this problem.Cu_(2-x)Se with mixed-valence is a potential candidate,the stable monoclinic structure of Cu2Se can be transformed into another stable cubic structure(x>0.15).Herein,Cu_(1.85)Se anode with mixed valence reveals the ultrahigh specific capacity of 247.8 mA·h/g at 2 A/g.Furthermore,the introduction of multi-walled carbon nanotubes(MWCNTs)into Cu1.85Se further improves the specific capacity(435 mA·h/g at 2 A/g).XRD shows that the introduction of MWCNTs can improve the reversibility via chemical interactions and accelerate the electron transfer in the Cu1.85Se/MWCNTs.Notably,the assembled symmetric supercapacitor(SC)device expresses a high energy density of 41.4 W·h/kg,and the capacity remains 83%even after 8000 charge/discharge cycles.This research demonstrates the great potential of developing high specific capacity anode materials for superior performance supercapacitor.
文摘Copper (Ⅱ) α-methacrylate reacts with triphenylphosphine to form whxed-valence copper (Ⅰ,Ⅱ) complex Cu4(CH2=C(CH3)COO)6(PPh3)4(CH3OH）2 in methanol solution. The crystal and molecular structure of the complex has been detendned by single crystal X-ray structural analysis. This material forms pale green crystals with triclinic symmetry, space group Pi, a=1 .3567(2) nm, b=1.3946 (3) nm, c=1.4569 (3) nm, α=66.069 (14)0, β=84.234 (14)0 γ=69.975 (13)0,R=0.0536.
基金supported by the National Natural Science Foundation of China(21908120 and 22109078)the Youth Innovation Team Project of Shandong Provincial Education Department(2019KJC023)。
文摘Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is vital to improve the kinetics of ammonia synthesis and obtain a less energy-intensive process.Herein,carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) was prepared and applied as an electrocatalyst for high-efficiency NRR.A dramatic faradaic efficiency(FE)of 36.93%and an NH_(3) production rate of 13.1μg h^(-1) mg_(cat)^(-1) were obtained at-0.3 V versus RHE,superior to nearly all Fe-based catalysts.Experiments and DFT calculations revealed that the superior performance was ascribed to the synergistic effect of mixed-valence iron pair,which braked the linear correlations to improve the kinetics of ammonia from collaborative hydrogenation and*NH_(3) separation.This work proves the feasibility of mixedvalence catalysts for nitrogen reduction and thus opening a new avenue towards artificial nitrogenfixation catalysts.
基金supported by the Natural Science Foundation of Shanxi province(2012021005-2)Technology Foundation for Selected Overseas of Shanxi
文摘Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964（5）, b = 10.2592, c = 10.5822（8） A, V = 933.01（9） A3, Z = 2, C_（30）H_（24）Br_4Cu_3N_（12）O_2P_2, M_r = 985.02, D_c = 1.753 g/cm3, F（000） = 4072 and μ（MoKα） = 0.746 mm^（-1）. The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 〉 2σ（I）. Cu（Ⅰ） is tetrahedrally coordinated and Cu（Ⅱ） center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N-H···O and N-H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.
基金Supported by the National Natural Science Foundation of China(No.2 0 1710 10 )
文摘A new layered mixed valence vanadium oxide, [CH 3NH 3] 2[(V ⅣO) 2(V ⅤO 4) 2], which contains interlamellar organic cations was prepared under hydrothermal conditions and its single crystal structure was determined. It crystallizes in a triclinic system with space group P 1, a =0 625 59(8) nm, b =0 639 84(9) nm, c =0 747 19(10) nm, α =78 718(2)°, β =80 099(2)°, γ =77 100(2). The compound contains mixed valence V 4+ /V 5+ vanadium oxide layers constructed from VO 4 tetrahedra, pairs of edge sharing VO 5 square pyramid and methylamine with protonated organic amines occupying the interlayer space.
文摘The mixed-valence isopolyanion Mo6O193- was investigated by means of cyclic voltammographic, in-situ FTIR and UV-Visible-Near-IR spectro-electrochemicalmethods in aprotic media. The experimental results indicate that the Mo6O193-was formed whereafter Mo6O193- was reduced, (E0' = - 0. 690 V, n = 1 ). The characteristic absorptions of Mo6O193- are 500 nm, 900 nm and 1100 nm in UV-VisibleNear-IR spectrum and 940 cm-1 in IR spectrum.
基金financial support from the "1000 Youth Talents Plan" the Natural Science Foundation of China (Nos. 21402107, 91427303)IIT Kanpur for funding
文摘A series of {2Fe3S} complexes bearing phosphino thioether chelating ligand were synthesized on the basis of Fe2（Me2pdt）（1,2-Cy2PC6H4SMe）（CO）4 （Me2pdt= Me2C（CH2S ）2, 1）. The disubstituted Fe（1）Fe（1） compound 1 exhibits a reversible one-electron redox even for [Fe（Ⅰ）Fe（Ⅱ）]＋/0 couple. Based on the oxidation of I to [1]＋, the tri-substituted [Fe（Ⅰ）Fe（Ⅱ）]＋ cationic complex [Fe2/Me2pdt）/1,2-Cy2PC6H4SMe） （PPh3）（CO）3]＋ （[2]＋） was synthesized. Reduction of [2]＋ provided the neutral tri-substituted Fe（l）Fe（1） compound 2. The substitution of the CO in I ligand by PPh3 results in an anodic shift of the Fe11Fe＋/Fe1Fe1 couple of470 mV. Most importantly, this substitution also leads to the Fe-Fe bonds in 1 and 2 with large Lewis basicity difference, i.e. △pKaMeCN ～ 10.
基金Project supported by the National Natural Science Foundation of China.
文摘 Reaction of [Mo3(CO)7(S,O-C6H4-1,2)3]2- with FeCl2 in MeCN at 60℃ affords a new Mo-Fe-S cluster complex containing MoO3S3 unit and mixed-valeut Mo atoms, [Et4N]2[Mo2Fe-(CO)4(O,S-C6H4-1,2)aCl2] (1). 1 is characterized by elemental analysis, IR, Mossbauer spectra, X-ray photoelectron spectra and mass spectra. And the structure of 1 is suggested as the structure which contains a [Mo(S,O-C6H4-1,2)3] unit of which the two of three sulfur atoms link to a Mo(CO)4-moiety and the three oxygen atoms are coordinated to a FeCl2 ligand.
基金This work was supported by the 973 Program of the MOST (001CB108906), the NNSFC (90206040, 20425313, 20521101, 20333070, and 20303021), the NSF of Fujian Province (2005HZ01-1) and the Chinese Academy of Sciences
文摘A mixed-valent hexanuclear complex [Cu^ⅡCu^Ⅰ2（pbi）2Br2]2 （pbi = （2-（2-pyridyl）-benzimidazole） exhibiting a dimeric unit bridged by two Br atoms was synthesized by hydrothermal reaction Interestingly, there exist intramolecular and intermolecular n^zstacking interactions as well as metalaromatic ring interactions in the title complex. The crystal belongs to the monoclinic system, space group P1, with a = 7.1061（9）, b = 12.1008（13）, c = 14.0711（17） A, α=91.742（8）,β=100.155（9）, γ=90.486（7）°, V = 1190.3（2） A^3, Z = 2, C48H32Br4CucoNt2, Mr = 1477.74, Dc= 2.061 g/cm^3, F（000） = 718, μ（MoKα） = 6.039 mm^-1, the final R = 0.0481 and wR = 0.0974 for 3426 observed reflections （I 〉 2σ（I））.
文摘A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].
文摘Five polynuclear monovalent and mixed-valence complexes of copper with 2-thiouracil were synthesized. They were characterized by the molar conductivity, electromc spectra, infrared spectroscopy, thermogravimetric and magnetic susceptibility measurements. Their coordination properties and tentative structures were discussed.
文摘The title compound was prepared by solid state reaction of LaCl_3/V inan evacuated silica tube where the silicon came from the reaction tube. The compoundcrystallizes in monoclinic space group C2/m with cell dimensions of a=13. 482 (7), b=5. 604(3), c=11. 091(3) A, β=100. 44(3)°, V=824(1) A3, Mr= 1274. 66 , Dc=5. 14 g/cm3, F(000) = 1150, μ- 13. 20 mm-1 and Z=2; final R=0. 061, Rw=0. 054for 1037 observed reflections (Ⅰ>3σ(Ⅰ) ) . It is isostructural with quasi-ZD Pr_4V_5Si_4O_(22)compound with the Ⅴ-Ⅴ distances across the shared VO6 octahedral edges of 2. 802 Aand vanadium ions show mixed-valence(Ⅲ/Ⅳ) with an average value of+ 3. 2.
