Molecular dynamics simulation is carried out to investigate the effects of cooling rate on the final configurations of silver after rapid solidification.The cooling rate for the formation of a silver amorphous phase i...Molecular dynamics simulation is carried out to investigate the effects of cooling rate on the final configurations of silver after rapid solidification.The cooling rate for the formation of a silver amorphous phase is determined by analyzing its pair distribution function,H-A bond index,and the largest crystal cluster.Further,the equilibrium structures of the subcritical nuclei and crystal clusters are studied.The results show that the solidified microstructure is composed of a mixture of crystal clusters and amorphous phases at a certain cooling rate range.The size of the largest crystal cluster decreases with the increasing cooling rate,and it completely disappears when the cooling rate exceeds a critical value.The structures of the subcritical nuclei and the largest crystal cluster are composed of lamellar structures of fcc and hcp atoms,indicating that the lamellar structure of fcc and hcp atoms in the silver crystal originates from nucleation,and not from the growth of crystals.展开更多
The title complex [^n BuSn（O）O2C（OH）CPh2]6.2H2O has been synthesized by the reaction of n-BuSn（O）OH with benzilic acid in 1：1 molar radio and characterized by IR, ^1H NMR spectra and elemental analysis. The cry...The title complex [^n BuSn（O）O2C（OH）CPh2]6.2H2O has been synthesized by the reaction of n-BuSn（O）OH with benzilic acid in 1：1 molar radio and characterized by IR, ^1H NMR spectra and elemental analysis. The crystal structure was determined by X-ray diffraction. It crystallizes in triclinic, space group PI with a = 1.3543（2）, b = 1.4593（2）, c = 1.5293（2） nm, α = 102.075 （2）,β = 115.571 （2）, γ = 93.308（3）°, Z = 1, V = 2.6282（7） nm^3, Mr = 2550.21, Dc = 1.611 g/cm^3,μ = 1.477 mm^-1, F（000） = 1280, R = 0.0309 and wR = 0.0729. The structure shows a distorted octahedral configuration with six-coordination for the central tin atom.展开更多
A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray...A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.展开更多
A new cluster {Mo3S4[NH2CH2CH(O)CH2NH2]3}(DTP)?(H2O)2?(DMF) (DTP = diethyldithiophosphate) has been synthesized via ligand substitution reaction of Mo3S4(DTP)4(H2O) with an alkaline ligand 1,3-diamino-2-propanol(DAPRO...A new cluster {Mo3S4[NH2CH2CH(O)CH2NH2]3}(DTP)?(H2O)2?(DMF) (DTP = diethyldithiophosphate) has been synthesized via ligand substitution reaction of Mo3S4(DTP)4(H2O) with an alkaline ligand 1,3-diamino-2-propanol(DAPROH) in a mixed organic solvent, and its crys- tal structure was determined with the following data: Mo3S6PC16H48O8N7, Mr = 977.76, triclinic, space group P1, Z = 2, a = 10.319(2), b = 12.843(3), c = 15.335(3) ?, α = 65.26(3), β = 82.18(3), γ = 70.67(3)o, V = 1741.7(6) ?3, Dc = 1.864 g/cm3, μ = 1.517 mm-1, F(000) = 988, the final R = 0.0794 and wR = 0.2111 for 6318 observed reflections (I>2σ(I)). The structure analysis indicates that all DTP ligands of Mo3S4(DTP)4(H2O) are replaced and each DAPRO molecule acts as a tri- dentate ligand chelating to each Mo atom of the Mo3S4 core. Different from the precursor, the clus- ter symmetry is elevated to C3. In addition, the UV-spectrum of the title compound was measured.展开更多
Ab initio total energy calculations are used to simulate the building of equiatomic solid APballoys (A=Li, Na, K) with A4Pb4 clusters which are particularly stable in the gas phase. Theeight clusters per unit cell wer...Ab initio total energy calculations are used to simulate the building of equiatomic solid APballoys (A=Li, Na, K) with A4Pb4 clusters which are particularly stable in the gas phase. Theeight clusters per unit cell were drawn together by shrinking the cell in stages, and allowingfull atomic relaxation at each stage. Charged Pb4 tetrahedral units dominate the structuraland electronic properties, and these units are remarkably robust and insensitive to their alkalienvironment. The stability of the Pb4 units diminishes as we progress from K to Li and lead totheir absence in the LiPb alloy in accordance with experiment. The distance between Pb4 unitsseems to be the critical factor responsible for the structural trends, which is determined by theatomic size of the alkali.展开更多
A new low-nuclear polymolybdate cluster [Cu_4~Ⅱ（opr）_2（Mo_（12）O_（40））]_n·2n H_2 O was successfully isolated by the introduction of flexible multidentate 1,1A-（1,3-propanediyl）bis[2-（2-pyridyl）benzimi...A new low-nuclear polymolybdate cluster [Cu_4~Ⅱ（opr）_2（Mo_（12）O_（40））]_n·2n H_2 O was successfully isolated by the introduction of flexible multidentate 1,1A-（1,3-propanediyl）bis[2-（2-pyridyl）benzimidazole ligand（opr）,（NH_4）_6Mo_7O_（24）·4H_2O,and copper（Ⅱ） ions under hydrothermal conditions. Single-crystal X-ray analysis reveals that the complex crystallizes in the P2_1/n space group with a = 13.8437（5）,b =19.3953（6）,c =15.7681（6） A,β =112.698（4）o,V = 3905.9（2） A^3,Z = 4,D_c = 2.502 g/cm^3,μ = 3.020 mm^-1,F（000） = 2824,the final R = 0.0352,wR = 0.0523 and S = 0.783 for 7111 observed reflections with I 〉 2σ（I）. The structure of the compound contains a new type of low-nuclear（Mo_（12）O_（40））^8-polymolybdate cluster. These dodecamolybdate anions are linked together through sharing edges to form a 1D molybdenum oxide chain. Its photocatalytic performance for methylene blue（MB） was also studied under UV irradiation.展开更多
A novel water cluster [Mn（phen）2·H2O·Cl]·p-FBA·3H2O （p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline） was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 1...A novel water cluster [Mn（phen）2·H2O·Cl]·p-FBA·3H2O （p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline） was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768（1）,b = 11.5960（1）,c = 12.9916（2） ,α = 101.816（2）,β = 95.397（2）,γ = 103.052（2）o,V = 1502.8（3） 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese（Ⅱ ） ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a （H2O）4 water cluster. This water pattern forms a cross-linked discrete ring. The steady （H2O）4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional （1D） structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.展开更多
The title compound has been synthesized by the reaction of(NH4)3VS4, CuBr and NMe4Br in pyridine and its structure was determined by singlecrystal X-ray diffraction. Crystallographic data: C40H40Br3Cu6N8S4V, M4= 1432....The title compound has been synthesized by the reaction of(NH4)3VS4, CuBr and NMe4Br in pyridine and its structure was determined by singlecrystal X-ray diffraction. Crystallographic data: C40H40Br3Cu6N8S4V, M4= 1432. 95,orthorhombic space group Fdd2, a= 29. 9519 (2), b=13. 4719 (2), c= 25. 8612 (4)A, V= 10435. 2 (4), Z= 8, Dc= 1.824 g/cm3, F(000)= 5616,μ(MoKa) =50.64 cm-1, the final R =0.091 and wR =0. 206 for those 3401 unique reflectionshaving . The crystal structure determination shows that the cluster consists of a tetrahedral VS4 core encapsulated by a distorted octahedral array of six copperatoms which have two different coordination geometries, trigonal and tetrahedral.展开更多
[Au13Ag12(μ-Br)1(μ3-Br)2 (Ph3P)10Br2] Br, monoclinic. space group C2/m, a = 36. 496(17). b=16. 878(7), c-=19. 772(9) A , β=99. 87(5)°, V=11998. 9 A3.Z=2. The final R(Rw) is 0. 097(0. 109) for 3779 reflections ...[Au13Ag12(μ-Br)1(μ3-Br)2 (Ph3P)10Br2] Br, monoclinic. space group C2/m, a = 36. 496(17). b=16. 878(7), c-=19. 772(9) A , β=99. 87(5)°, V=11998. 9 A3.Z=2. The final R(Rw) is 0. 097(0. 109) for 3779 reflections with I>3σ(I). The structure can he considered as two icosahedral cluster units (AurAg6) sharing one vertex and linked hy six bromine atoms. The Au - Au, Au - Ag. and Ag-Ag distances fall in the ranges of 2. 69-2. 96. 2. 84-3. 02. and 2. 92-3. 26 A, respectively.展开更多
A novel 2D layered compound （H4HMTA）2（H3O）2{Na2（H2O）6（H2W12O42） }C12-11H2O （HMTA = hexamethylenetetraamine） has been synthesized and characterized by elemental analyses, IR, UV-Vis and X-ray diffraction. C12...A novel 2D layered compound （H4HMTA）2（H3O）2{Na2（H2O）6（H2W12O42） }C12-11H2O （HMTA = hexamethylenetetraamine） has been synthesized and characterized by elemental analyses, IR, UV-Vis and X-ray diffraction. C12H74CI2N8Na2O61W12 （Mr = 3629.87） crystallizes in the triclinic system, space group P1 with a = 10.5518（2）, b = 12.1837（2）, c = 14.3088（2） A, α = 112.9470（10）, β = 93.1310（10）, γ= 106.1530（10）°, V = 1599.20（5）A3 Dc = 3.769 g.cm^-3, Z = 1, μ（MoKα） = 21.705 mm^-1, F（000） = 1634, the final R = 0.0287 and wR = 0.0686 for 5846 observed reflections with I 〉 2σ（I）. The 2D layered network is assembled from paradodecatungstate clusters linked by simple sodium-oxo bridging groups. The compound exhibits electrocatalytic activities toward both reduction and oxidation of nitrite.展开更多
The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21...The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563（3）, b = 8.9547（18）, c = 17.846（4） A, β = 101.29（3）°, V = 2438.9（9） A^3, Z = 4, Dc = 1.878 g/cm^3, T = 193（2） K, C20H30ClCuMo2S4, Mr = 689.60, F（000） = 1376, μ（MoKa） = 2.335 mm ^-1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I 〉 20-（I）. In the structure of 2, one [（η^5-C5Me5）2Mo2（μ-S）2S] moiety and one CuCI unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one ,μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519（7） and 2.7689（8） A, respectively.展开更多
The title compound has been synthesized by reaction of (NH4)3VS4,CuCl, and PBu3 in CH2Cl2 and its structure was determined by single crystal X-raydiffraction. Crystallographic data: C72 H162 Cu6O2P6S8V2, Mr= 1985. 57,...The title compound has been synthesized by reaction of (NH4)3VS4,CuCl, and PBu3 in CH2Cl2 and its structure was determined by single crystal X-raydiffraction. Crystallographic data: C72 H162 Cu6O2P6S8V2, Mr= 1985. 57, monoclinicspace group C2/c, a= 17. 864(3), b= 25. 946(8), c= 24.071 (7),β= 112. 79(2)°,V = 10285. 9, Z= 4, Dc= 1. 28 g/cm3, F(000) = 4192, μ(MoKa) = 16. 7 cm-1,the final R=0.065 and Rw =0.074 for 4051 unique reflections with I> 3σ(I). Thestructure can be described as a metal-sulfur dodecahedral cage fused by two incompletecubane-like VS3Cu3 units connected by Cu - S bonds. The Cu - S bonds within theasymmetric VS3Cu3 unit are slightly shorter than those linking the two centrosymmetrically related VS3Cu3 units. The six copper and two vanadium atoms display asomewhat distorted cubane array with a μ4-S atom on each face of the metal cubane.展开更多
A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belong...A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 13.6345（2）, b = 13.7805（2）, c = 14.5400（1）A, α = 107.078（1）, β = 113.380（1）, γ = 96.310（1）°, C25H45Mo3- N2O9P3S10, Mr = 1218.96, V = 2315.75（5） A^3, Z = 2, Dc = 1.748 g/cm^3, μ = 1.399, F（000） = 1224, R = 0.0425 and wR = 0.1144 for 6335 observed reflections （I 〉 2σ（I））. 31^P NMR spectrum has been measured with the resonance 110.050 and 108.783 （2：1）.展开更多
A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-cr...A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.展开更多
A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental anal...A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound 6 crystallizes in monoclinic, space group C2/c with a = 26.9236（18）, b = 15.2553（8）, c = 24.6237（13） , β = 103.0680（10）°, V = 9851.7（10）3, C58H66Ag6Cl6N20O3S6, Mr = 2143.59, Dc = 1.445 g/cm3, μ（MoKα） = 1.503 mm-1, F（000） = 4232, Z = 4, the final R = 0.0565 and wR = 0.1654 for 5831 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Similar to the structure of the compounds we have reported, compound 6 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L6 （L6 = 2-chloro-1-benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L66 cluster. The luminescence property of compound 6 was investigated at room temperature and compared with other similar compounds in order to find the factors influencing their luminescent property.展开更多
A new tetranuclear cluster [Co4（bm）6C12]＇（H20）2-（CH3OH） （1, Hbm is （1H-benzi- midazol-2-yl）-methanol） has been synthesized by solvothermal method and structurally determined by IR, elemental analysis, and s...A new tetranuclear cluster [Co4（bm）6C12]＇（H20）2-（CH3OH） （1, Hbm is （1H-benzi- midazol-2-yl）-methanol） has been synthesized by solvothermal method and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. Complex 1 belongs to monoclinie space group P21/n with a = 21.1713（5）, b = 12.7948（3）, c = 24.0195（9） А, β = 95.309（3）°, V = 6478.6（3） A3, Z = 4, F（000） = 2568, Dc = 1.289 g.cm-3, Mr = 1257.63,μ= 9.096 mm-I, S = 1.000, the final R = 0.0861 and wR = 0.2552 for 4956 observed reflections with 1 〉 20（/）. Two connected face-sharing cubes are observed in the framework of 1, each with one vertex missing. Complex 1 forms a 2-D network through N-H...O hydrogen bonds. The apparent holes can be observed.展开更多
Reaction of (NH_4)_2MoS_4 with AgI in α-MePy gives the title com- pound,an X-ray analysis of which shows that the molecule forms a one-dimensional polymeric chain with continuous metal-metal bonds.
A new hetero-six-nuclear cluster was synthesized and determined by X-ray diffraction technique. The four-carboxylate groups are bound to the Cu(II) atoms to form Cu(OR)4Cu paddle-wheel-type cage between two DMF as the...A new hetero-six-nuclear cluster was synthesized and determined by X-ray diffraction technique. The four-carboxylate groups are bound to the Cu(II) atoms to form Cu(OR)4Cu paddle-wheel-type cage between two DMF as the basis for the cluster. The distance of two copper(II) atoms is 2.642 ?, and they are bridged by the carboxylate groups. A huge system plane was auto-assembled by four host molecules and two Cu (II) ions, which was observed in the crystal structure.展开更多
The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffrac...The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffraction method.It crystallizes in the orthorhombic space group Pnna with cell parameters:Mr=1361.6,a=13.792(4), b=17.957(3),c=20.974(9) ,V=5194(2) ~3,Z=4,Dc=1.74/cm^3,F(OOO)=2704,μ(MoK ) =11.0/cm,R=0.074.展开更多
Reaction of dimers of (R) thionophosphine sulfide (R = P - C6H4OMe,SMe ) with Co, (CO), yields the novel hexacobalt cluster [Co'(μ3, -S)2, (CO) 14 (μ4 -μ4- and the trinuclear clusterPSCH,)J 2' In 1, tw0 Co3...Reaction of dimers of (R) thionophosphine sulfide (R = P - C6H4OMe,SMe ) with Co, (CO), yields the novel hexacobalt cluster [Co'(μ3, -S)2, (CO) 14 (μ4 -μ4- and the trinuclear clusterPSCH,)J 2' In 1, tw0 Co3S(C0)7 units linked by a novel phosphido-thio1ato bifunc-tiona1 bridging p'-SPR ligand as backbone.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.51071115,50671075)the National Basic Research Program of China("973"Program)(Grant No.2006CB605202)
文摘Molecular dynamics simulation is carried out to investigate the effects of cooling rate on the final configurations of silver after rapid solidification.The cooling rate for the formation of a silver amorphous phase is determined by analyzing its pair distribution function,H-A bond index,and the largest crystal cluster.Further,the equilibrium structures of the subcritical nuclei and crystal clusters are studied.The results show that the solidified microstructure is composed of a mixture of crystal clusters and amorphous phases at a certain cooling rate range.The size of the largest crystal cluster decreases with the increasing cooling rate,and it completely disappears when the cooling rate exceeds a critical value.The structures of the subcritical nuclei and the largest crystal cluster are composed of lamellar structures of fcc and hcp atoms,indicating that the lamellar structure of fcc and hcp atoms in the silver crystal originates from nucleation,and not from the growth of crystals.
基金This work was supported by the Natural Science Foundation of Hunan Province(05JJ40015) and Project supported by Science Foundation of Hengyang Normal University of China (2004D16)
文摘The title complex [^n BuSn（O）O2C（OH）CPh2]6.2H2O has been synthesized by the reaction of n-BuSn（O）OH with benzilic acid in 1：1 molar radio and characterized by IR, ^1H NMR spectra and elemental analysis. The crystal structure was determined by X-ray diffraction. It crystallizes in triclinic, space group PI with a = 1.3543（2）, b = 1.4593（2）, c = 1.5293（2） nm, α = 102.075 （2）,β = 115.571 （2）, γ = 93.308（3）°, Z = 1, V = 2.6282（7） nm^3, Mr = 2550.21, Dc = 1.611 g/cm^3,μ = 1.477 mm^-1, F（000） = 1280, R = 0.0309 and wR = 0.0729. The structure shows a distorted octahedral configuration with six-coordination for the central tin atom.
基金financially supported by the Foundation of Fujian Educational Committee(JA14348)
文摘A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.
基金This work was supported by the State Key Basic Research and Development Plan of China (001CB108906)the NNSF of China (20173063) NSF of Fujian Province (E0020001)
文摘A new cluster {Mo3S4[NH2CH2CH(O)CH2NH2]3}(DTP)?(H2O)2?(DMF) (DTP = diethyldithiophosphate) has been synthesized via ligand substitution reaction of Mo3S4(DTP)4(H2O) with an alkaline ligand 1,3-diamino-2-propanol(DAPROH) in a mixed organic solvent, and its crys- tal structure was determined with the following data: Mo3S6PC16H48O8N7, Mr = 977.76, triclinic, space group P1, Z = 2, a = 10.319(2), b = 12.843(3), c = 15.335(3) ?, α = 65.26(3), β = 82.18(3), γ = 70.67(3)o, V = 1741.7(6) ?3, Dc = 1.864 g/cm3, μ = 1.517 mm-1, F(000) = 988, the final R = 0.0794 and wR = 0.2111 for 6318 observed reflections (I>2σ(I)). The structure analysis indicates that all DTP ligands of Mo3S4(DTP)4(H2O) are replaced and each DAPRO molecule acts as a tri- dentate ligand chelating to each Mo atom of the Mo3S4 core. Different from the precursor, the clus- ter symmetry is elevated to C3. In addition, the UV-spectrum of the title compound was measured.
文摘Ab initio total energy calculations are used to simulate the building of equiatomic solid APballoys (A=Li, Na, K) with A4Pb4 clusters which are particularly stable in the gas phase. Theeight clusters per unit cell were drawn together by shrinking the cell in stages, and allowingfull atomic relaxation at each stage. Charged Pb4 tetrahedral units dominate the structuraland electronic properties, and these units are remarkably robust and insensitive to their alkalienvironment. The stability of the Pb4 units diminishes as we progress from K to Li and lead totheir absence in the LiPb alloy in accordance with experiment. The distance between Pb4 unitsseems to be the critical factor responsible for the structural trends, which is determined by theatomic size of the alkali.
基金supported by the National Natural Science Foundation of China(No.21201128)the Science Research Founds of Education Department of Liaoning Province(L2014596)
文摘A new low-nuclear polymolybdate cluster [Cu_4~Ⅱ（opr）_2（Mo_（12）O_（40））]_n·2n H_2 O was successfully isolated by the introduction of flexible multidentate 1,1A-（1,3-propanediyl）bis[2-（2-pyridyl）benzimidazole ligand（opr）,（NH_4）_6Mo_7O_（24）·4H_2O,and copper（Ⅱ） ions under hydrothermal conditions. Single-crystal X-ray analysis reveals that the complex crystallizes in the P2_1/n space group with a = 13.8437（5）,b =19.3953（6）,c =15.7681（6） A,β =112.698（4）o,V = 3905.9（2） A^3,Z = 4,D_c = 2.502 g/cm^3,μ = 3.020 mm^-1,F（000） = 2824,the final R = 0.0352,wR = 0.0523 and S = 0.783 for 7111 observed reflections with I 〉 2σ（I）. The structure of the compound contains a new type of low-nuclear（Mo_（12）O_（40））^8-polymolybdate cluster. These dodecamolybdate anions are linked together through sharing edges to form a 1D molybdenum oxide chain. Its photocatalytic performance for methylene blue（MB） was also studied under UV irradiation.
基金supported by the Postgraduate Foundation of Taishan University (No. Y07-2-16)
文摘A novel water cluster [Mn（phen）2·H2O·Cl]·p-FBA·3H2O （p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline） was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768（1）,b = 11.5960（1）,c = 12.9916（2） ,α = 101.816（2）,β = 95.397（2）,γ = 103.052（2）o,V = 1502.8（3） 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese（Ⅱ ） ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a （H2O）4 water cluster. This water pattern forms a cross-linked discrete ring. The steady （H2O）4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional （1D） structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.
文摘The title compound has been synthesized by the reaction of(NH4)3VS4, CuBr and NMe4Br in pyridine and its structure was determined by singlecrystal X-ray diffraction. Crystallographic data: C40H40Br3Cu6N8S4V, M4= 1432. 95,orthorhombic space group Fdd2, a= 29. 9519 (2), b=13. 4719 (2), c= 25. 8612 (4)A, V= 10435. 2 (4), Z= 8, Dc= 1.824 g/cm3, F(000)= 5616,μ(MoKa) =50.64 cm-1, the final R =0.091 and wR =0. 206 for those 3401 unique reflectionshaving . The crystal structure determination shows that the cluster consists of a tetrahedral VS4 core encapsulated by a distorted octahedral array of six copperatoms which have two different coordination geometries, trigonal and tetrahedral.
文摘[Au13Ag12(μ-Br)1(μ3-Br)2 (Ph3P)10Br2] Br, monoclinic. space group C2/m, a = 36. 496(17). b=16. 878(7), c-=19. 772(9) A , β=99. 87(5)°, V=11998. 9 A3.Z=2. The final R(Rw) is 0. 097(0. 109) for 3779 reflections with I>3σ(I). The structure can he considered as two icosahedral cluster units (AurAg6) sharing one vertex and linked hy six bromine atoms. The Au - Au, Au - Ag. and Ag-Ag distances fall in the ranges of 2. 69-2. 96. 2. 84-3. 02. and 2. 92-3. 26 A, respectively.
基金supported by the Natural Science Foundation of Fujian Province (No. E0420001)NCETFJ (No. 07FJCR0168)
文摘A novel 2D layered compound （H4HMTA）2（H3O）2{Na2（H2O）6（H2W12O42） }C12-11H2O （HMTA = hexamethylenetetraamine） has been synthesized and characterized by elemental analyses, IR, UV-Vis and X-ray diffraction. C12H74CI2N8Na2O61W12 （Mr = 3629.87） crystallizes in the triclinic system, space group P1 with a = 10.5518（2）, b = 12.1837（2）, c = 14.3088（2） A, α = 112.9470（10）, β = 93.1310（10）, γ= 106.1530（10）°, V = 1599.20（5）A3 Dc = 3.769 g.cm^-3, Z = 1, μ（MoKα） = 21.705 mm^-1, F（000） = 1634, the final R = 0.0287 and wR = 0.0686 for 5846 observed reflections with I 〉 2σ（I）. The 2D layered network is assembled from paradodecatungstate clusters linked by simple sodium-oxo bridging groups. The compound exhibits electrocatalytic activities toward both reduction and oxidation of nitrite.
基金The project was supported by the NNSFC (No. 20525101)the NSF of Jiangsu Province (No. BK2004205)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20050285004)the State Key Laboratory of Organometallic Chemistry (No. 06-26)
文摘The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563（3）, b = 8.9547（18）, c = 17.846（4） A, β = 101.29（3）°, V = 2438.9（9） A^3, Z = 4, Dc = 1.878 g/cm^3, T = 193（2） K, C20H30ClCuMo2S4, Mr = 689.60, F（000） = 1376, μ（MoKa） = 2.335 mm ^-1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I 〉 20-（I）. In the structure of 2, one [（η^5-C5Me5）2Mo2（μ-S）2S] moiety and one CuCI unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one ,μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519（7） and 2.7689（8） A, respectively.
文摘The title compound has been synthesized by reaction of (NH4)3VS4,CuCl, and PBu3 in CH2Cl2 and its structure was determined by single crystal X-raydiffraction. Crystallographic data: C72 H162 Cu6O2P6S8V2, Mr= 1985. 57, monoclinicspace group C2/c, a= 17. 864(3), b= 25. 946(8), c= 24.071 (7),β= 112. 79(2)°,V = 10285. 9, Z= 4, Dc= 1. 28 g/cm3, F(000) = 4192, μ(MoKa) = 16. 7 cm-1,the final R=0.065 and Rw =0.074 for 4051 unique reflections with I> 3σ(I). Thestructure can be described as a metal-sulfur dodecahedral cage fused by two incompletecubane-like VS3Cu3 units connected by Cu - S bonds. The Cu - S bonds within theasymmetric VS3Cu3 unit are slightly shorter than those linking the two centrosymmetrically related VS3Cu3 units. The six copper and two vanadium atoms display asomewhat distorted cubane array with a μ4-S atom on each face of the metal cubane.
基金This work was supported by the State Key Basic Research and Development Plan of China (001CB108906)the YIF (2005J060) and NSF (2006J0015) of Fujian Provincethe Major Special Foundation of Fujian Province (2005HZ1027 and 2005HZ01-1)
文摘A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 13.6345（2）, b = 13.7805（2）, c = 14.5400（1）A, α = 107.078（1）, β = 113.380（1）, γ = 96.310（1）°, C25H45Mo3- N2O9P3S10, Mr = 1218.96, V = 2315.75（5） A^3, Z = 2, Dc = 1.748 g/cm^3, μ = 1.399, F（000） = 1224, R = 0.0425 and wR = 0.1144 for 6335 observed reflections （I 〉 2σ（I））. 31^P NMR spectrum has been measured with the resonance 110.050 and 108.783 （2：1）.
基金the Natural Science Foundation of China Fujian Province and Chinese Academy of Sciences.
文摘A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.
基金supported by the National Science and Technology Support Program (2012BAC12B03)the Postdoctoral Science Foundation of Central South Universitythe Fundamental Research Funds for the Central Universities (No. 2012QNZT001)
文摘A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound 6 crystallizes in monoclinic, space group C2/c with a = 26.9236（18）, b = 15.2553（8）, c = 24.6237（13） , β = 103.0680（10）°, V = 9851.7（10）3, C58H66Ag6Cl6N20O3S6, Mr = 2143.59, Dc = 1.445 g/cm3, μ（MoKα） = 1.503 mm-1, F（000） = 4232, Z = 4, the final R = 0.0565 and wR = 0.1654 for 5831 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Similar to the structure of the compounds we have reported, compound 6 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L6 （L6 = 2-chloro-1-benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L66 cluster. The luminescence property of compound 6 was investigated at room temperature and compared with other similar compounds in order to find the factors influencing their luminescent property.
基金financially supported by the National Natural Science Foundation of China(No.21161006)Program for Excellent Talents in Guangxi Higher Education Institutions(Gui Jiao Ren[2012]41)Program of the first session backbone teacher of Guangxi of China
文摘A new tetranuclear cluster [Co4（bm）6C12]＇（H20）2-（CH3OH） （1, Hbm is （1H-benzi- midazol-2-yl）-methanol） has been synthesized by solvothermal method and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. Complex 1 belongs to monoclinie space group P21/n with a = 21.1713（5）, b = 12.7948（3）, c = 24.0195（9） А, β = 95.309（3）°, V = 6478.6（3） A3, Z = 4, F（000） = 2568, Dc = 1.289 g.cm-3, Mr = 1257.63,μ= 9.096 mm-I, S = 1.000, the final R = 0.0861 and wR = 0.2552 for 4956 observed reflections with 1 〉 20（/）. Two connected face-sharing cubes are observed in the framework of 1, each with one vertex missing. Complex 1 forms a 2-D network through N-H...O hydrogen bonds. The apparent holes can be observed.
文摘Reaction of (NH_4)_2MoS_4 with AgI in α-MePy gives the title com- pound,an X-ray analysis of which shows that the molecule forms a one-dimensional polymeric chain with continuous metal-metal bonds.
基金We are grateful to the National Natural Science Foundation of China(project 20072034)the Natural Science Foundation of Henan province and the Foundation for Young Teacher in Zhenzhou University for the financial support.
文摘A new hetero-six-nuclear cluster was synthesized and determined by X-ray diffraction technique. The four-carboxylate groups are bound to the Cu(II) atoms to form Cu(OR)4Cu paddle-wheel-type cage between two DMF as the basis for the cluster. The distance of two copper(II) atoms is 2.642 ?, and they are bridged by the carboxylate groups. A huge system plane was auto-assembled by four host molecules and two Cu (II) ions, which was observed in the crystal structure.
基金Work supported by the National Natural Science Foundation of China(NNSFC)
文摘The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffraction method.It crystallizes in the orthorhombic space group Pnna with cell parameters:Mr=1361.6,a=13.792(4), b=17.957(3),c=20.974(9) ,V=5194(2) ~3,Z=4,Dc=1.74/cm^3,F(OOO)=2704,μ(MoK ) =11.0/cm,R=0.074.
文摘Reaction of dimers of (R) thionophosphine sulfide (R = P - C6H4OMe,SMe ) with Co, (CO), yields the novel hexacobalt cluster [Co'(μ3, -S)2, (CO) 14 (μ4 -μ4- and the trinuclear clusterPSCH,)J 2' In 1, tw0 Co3S(C0)7 units linked by a novel phosphido-thio1ato bifunc-tiona1 bridging p'-SPR ligand as backbone.
