The title complex [Ag（carbene）2]2[Ag2Br4] has been synthesized by the reaction of Ag2O with 1-ethyl-3-benyl-imidazolium bromide in DMSO at room temperature, and characterized by elemental analysis, 1H NMR and single...The title complex [Ag（carbene）2]2[Ag2Br4] has been synthesized by the reaction of Ag2O with 1-ethyl-3-benyl-imidazolium bromide in DMSO at room temperature, and characterized by elemental analysis, 1H NMR and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P with a = 10.1597（10）, b =11.0646（11）, c = 13.0245（14） , α = 102.230（2）, β = 90.606, γ = 113.9250（10）o, V = 1300.3（2） 3, Mr = 748.06, Z = 2, Dc = 1.911 g/cm3, μ（MoKα） = 4.60 mm-1 and F（000） = 728. The structure was refined to R = 0.0316 and wR = 0.0835 for 3744 observed reflections with I 〉 2σ（I）. The title compound crystallizes as a centrosymmetric tetranuclear compound. One half of the molecule comprises the asymmetric unit of the structure. The Ag（1） atom is nearly linear or T-shaped when the Ag（1）-Ag（2） interaction is taken into consideration, which is bi-coordinated by two carbene carbon atoms. The Ag（2） atom adopts tetrahedral geometry. The catalytic behavior of the title complex has been investigated, and the results indicate it has a highly catalytic activation for L-lactide polymerization.展开更多
A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by e...A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal gravimetry （TG）, fluorescent emission and single-crystal X-ray diffraction. Its crystal structure is of monoclinic, space group P2 1/c with a = 9.8897（8）, b = 14.2506（12）, c = 26.384（2） ,A, β = 94.8940（10）°, V = 3704.8（5） A3 Z = 2, C86H52N16O16S2Zn4, Mr = 1891.04, Dc = 1.695 g/cm^3, μ= 1.423 mm^-1, F（000） = 1920, GOOF = 1.039, the final R = 0.0358 and wR = 0.0872 for 6038 observed reflections with I 〉 2σ（I）. In 1, ＂cage-like＂ tetranuclear clusters of [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] are further stacked through π-π interactions to generate a 3D supramolecular network.展开更多
The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur...The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.展开更多
The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2...The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2·2H2O with 2-amino-1,3-thiazole in methanol and characterized by IR spectra and X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=9.7137（2）,b=10.7005（2）,c=14.6505（2）,α=83.9550（10）,β=82.0930（10）,γ=67.1640（10）°,V=1387.84（4）3,Mr=883.43,Z=2,μ=3.927 mm-1,Dc=2.1144 g/cm3,F（000）=868,R=0.0332 and wR=0.0814.The complex contains a tetrahedron of four CuII atoms coordinating to a central μ4-O atom,with the six edges of the tetrahedron bridged by six Cl atoms.The Cu-O bond distances range from 1.910（2） to 1.918（2）,Cu-Cl from 2.3501（11） to 2.5924（10）,and Cu-Cu from 3.1003（6） to 3.1663（6）.The coordination geometries of the four coppers distort from trigonal bipramid to tetragonal pyramid with different distortion factors.The free animo groups of the ligands result in a lot of N-H···Cl and N-H···N intra-and intermolecular hydrogen bonds.展开更多
A novel tetranuclear nickel（II） complex [NiaL2（DMF）2（H20）2＇2DMF] （1, H4L = azo-enolic-2-hydroxybenzamide, DMF = N,N-dimethyl-formamide） has been synthesized and characterized by elemental analysis, UV, IR and...A novel tetranuclear nickel（II） complex [NiaL2（DMF）2（H20）2＇2DMF] （1, H4L = azo-enolic-2-hydroxybenzamide, DMF = N,N-dimethyl-formamide） has been synthesized and characterized by elemental analysis, UV, IR and X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P21/n with a = 8.8944（11）, b = 14.4583（18）, c = 18.097（2） A, fl = 90.00（2）, Z = 2 , V = 2327.2（5） A3, C40H48NI2Ni4OI4, Mr = 1155.66, Dc= 1.649 g/cm3,μ=1.672 mm1, F（000） = 1192, R = 0.0392 and wR = 0.0958. The local coordination environment around the nickel ions exist a distorted octahedral and quadrangle geometry in the molecular structure. Complex 1 exhibits strong photoluminescent emission in the ultraviolet region at room temperature. The electrochemical studies reveal that redox of Nia＋/Ni2＋ in the complex is a quasi-reversible process.展开更多
Two novel zinc（Ⅱ） coordination polymers, [Zn2（BCB）（CH3OH）（μ3-OH）]n（1） and {[Zn2（BCB）（μ3-OH）（H2O）2]·CH3OH}n （2）, have been constructed from 3,5-bis（2-carboxylphenoxy）benzoic acid（H3BCB） an...Two novel zinc（Ⅱ） coordination polymers, [Zn2（BCB）（CH3OH）（μ3-OH）]n（1） and {[Zn2（BCB）（μ3-OH）（H2O）2]·CH3OH}n （2）, have been constructed from 3,5-bis（2-carboxylphenoxy）benzoic acid（H3BCB） and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. Structural analysis reveals that complexes 1 and 2 are both 1D polymeric chains with unprecedented tetranuclear {Zn4（COO）4（μ3-OH）2} clusters, which were further expanded into a 2D structure. Fluorescence measurements show that 1 and 2 have highly selective and sensitive detection of nitrobenzene.展开更多
A novel oxamide-bridged trimeric tetranuclear complex 1 incorporating a macro- cyclic oxamide of formula {[(CuL)3Mn](ClO4)2}3 (macrocyclic oxamide L = 2,3-dioxo-5,6,14,15- dibenzo-1,4,8,12-tetraazacyclopentadeca-7,12-...A novel oxamide-bridged trimeric tetranuclear complex 1 incorporating a macro- cyclic oxamide of formula {[(CuL)3Mn](ClO4)2}3 (macrocyclic oxamide L = 2,3-dioxo-5,6,14,15- dibenzo-1,4,8,12-tetraazacyclopentadeca-7,12-diene) was prepared and structurally characterized. The compound [(CuL)3Mn](ClO4)2 crystallizes in the trigonal system, space group P 3 with a = 22.434(17), b = 22.434(17), c = 18.82(2) ?, α = β = 90, γ = 120o, V = 8203(13) ?3, Z = 6, Dc = 1.751g/cm3, μ(MoKα) = 1.557, F(000) = 4392, the final R = 0.083 and wR = 0.1727 for 9604 obser- ved reflections with I > 2σ(I). The single-crystal X-ray analysis shows that 1 is a trimeric complex. There are three similar constitutes, dissimilar conformations and asymmetrically independent ‘building-block’ [(CuL)3Mn] in one crystal cell of the title complex 1.展开更多
The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1....The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.展开更多
The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1....The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.展开更多
The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central ...The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central μ_4-O atom and the four Nd atoms.The results of calculation show that the μ_4-O atom uses its sp^3 valence orbitals to contribute four O-Nd bonding MOs with character of multicenter bond apparent- ly.The Mulliken population analysis shows that the overlap population between Nd atoms is almost equal to zero,therefore there is no direct metal-metal bond between Nd atoms.The coordination number of Nd in the complex is discussed briefly.展开更多
A unique metal-organic framework [Cd2（L）1.5（μ3-OH）（H2 O）2 ]·2H2 O（1, H2 L = 2,5-dibenzoylterephthalic acid） has been synthesized under hydrothermal conditions, and characterized by single-crystal X-ray d...A unique metal-organic framework [Cd2（L）1.5（μ3-OH）（H2 O）2 ]·2H2 O（1, H2 L = 2,5-dibenzoylterephthalic acid） has been synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffractions, elemental analyses, IR spectra and fluorescence spectrum. The compound is of triclinic system, space group P1, C33 H27 CdO14, Mr = 870.33, a = 12.2939（17）, b = 12.5135（9）, c = 13.2046（10）, α = 115.3190（10）, β = 96.9140（10）, γ = 109.7950（10）°, V = 1641.6（3）3, Z = 2, Dc = 1.761 g/cm3, F（000） = 862, μ（MoK） = 1.366 mm-1, Rint = 0.0148, R = 0.0240 and wR = 0.0639 for 5995 observed reflections with I 〉 2σ（I）. X-ray analysis shows that the title complex exhibits a 3D framework with（412·63） topology, in which the tetra-nuclear [Cd4（μ3-OH）2 ] clusters act as 6-connected nodes, and the L ligands can be simplified to be linear connectors. Moreover, the thermal stability and fluorescence have been studied in detail.展开更多
One novel Co（II） coordination polymer, namely [Co4（L）6（NO3）2] （1） was prepared by solvothermal reactions of Co（NO3）2 with a （E）-2-[2-（3-thienyl）ethenyl]-8-quinolinol ligand （HL）, which has been determi...One novel Co（II） coordination polymer, namely [Co4（L）6（NO3）2] （1） was prepared by solvothermal reactions of Co（NO3）2 with a （E）-2-[2-（3-thienyl）ethenyl]-8-quinolinol ligand （HL）, which has been determined by single-crystal X-ray diffraction analyses and further characterized by means of elemental analyses, IR spectra, PXRD and thermogravimetric analyses （TGA）. The core structure of complex 1 is an incomplete dicubane-like tetranuclear Co（II） cluster, which is surrounded by six 8-hydroxy-quinolinate-based ligands and two nitrate ligands. Weak S-O interactions between the thienyl groups and nitrate ligands extend the adjacent tetranuclear CoOI） clusters into a supramolecular （4, 4） net structure. Magnetic measurement indicates that the coupling within both molecules is overall antiferromagnetic.展开更多
The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsa...The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.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
A tetranuclear zinc benzoate Zn_(4)O(C6H5CO_(2))6 was synthesized and characterized by X-ray single crystal determination.It crystallizes in cubic,space groupIa-3d.Its crystal cell is very large,a=4.10063(18)nm,V=68.9...A tetranuclear zinc benzoate Zn_(4)O(C6H5CO_(2))6 was synthesized and characterized by X-ray single crystal determination.It crystallizes in cubic,space groupIa-3d.Its crystal cell is very large,a=4.10063(18)nm,V=68.953(5)nm3 and Z=48.The structure is composed of discrete Zn_(4)O(C6H5CO_(2))6 molecules.In each molecule,four zinc atoms are held together by a central oxygen atom,which results in the formation of a regular tetrahedron.All benzoate ligands coordinate to zinc atoms in a bidentate bridging mode.Each zinc atom is in a slightly distorted tetrahedral geometry,coordinated by three benzoate oxygen atoms and the central oxygen atom.The intermolecular interactions result in the formation of a three-dimensional supramolecular framework,with non-intersecting parallel channels.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
The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethan...The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in the presence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c, Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4; Dc=1.78g/cm^3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]cluster core and t-(dtp)^(-1)ligands are retained and only μ-bridged(dtp)^(-1)ligands are substituted by(C_6H_5CO_2)^(-1)in the substitution reaction,thus producing the new title cluster compound,the structure of which contains two species of bidentate ligand.展开更多
A new tetranuclear silver（I） complex with the formula of [Ag4（MMPzA）2（dmPz）4（H2DPC）2]（H2O）4（1, MMPz A = mono（3,5-bimethyl-pyrazolmethyl）amine）, dm Pz = 3,5-dimethylpyrazole, H2DPC = pyridine-3,4-dicarbox...A new tetranuclear silver（I） complex with the formula of [Ag4（MMPzA）2（dmPz）4（H2DPC）2]（H2O）4（1, MMPz A = mono（3,5-bimethyl-pyrazolmethyl）amine）, dm Pz = 3,5-dimethylpyrazole, H2DPC = pyridine-3,4-dicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction method. The title complex crystallizes in the triclinic system, space group P1 with a = 10.5532（13）, b = 11.5071（18）, c = 13.3951（17） A, α = 97.3190（10）, β = 106.7360（10）, γ = 108.0770（10）o, V = 1438.3（3） A3, Z = 1, Dc = 1.691 g/cm3, F（000） = 736, μ = 1.421 mm-1, the final R = 0.0400 and w R = 0.0942 for 5097 observed reflections（I 〉 2σ（I））. The intermolecular hydrogen bonding interaction extends the complex into a 1D chain structure. In addition, the complex was tested in vitro for its antibacterial activity and it exhibited significant activity, especially against penicillium.展开更多
In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip ...In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine), are synthesized from the reaction of well characterized Lewis base [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>O<sub>2</sub>] with carbon dioxide as a Lewis acid in CH<sub>2</sub>Cl<sub>2</sub>. These carbonato-derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH<sub>2</sub>Cl<sub>2</sub>or phNO<sub>2</sub>. Cryoscopic measurements support tetranuclear structure for all of them. Electronic spectra in the near infrared with high molecular absorptivity may be explained for tetranuclear cuban structure to fulfil 3 halo-ligands for each copper centre in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>]. The EPR spectra for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] complexes are axial type of spectra (d<sub>x2-y2</sub> G.S) suggesting elongated tetragonal distortion for all of them. Cyclic voltammograms for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] are irreversible in character. These tetranuclear carbonato complexes show catalytical activity. They initiate the oxidation of 2,6-dimethylphenol (DMP) to 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ).展开更多
Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions an...Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.展开更多
基金Sichuan Application Basic Foundation (2009JY0075)
文摘The title complex [Ag（carbene）2]2[Ag2Br4] has been synthesized by the reaction of Ag2O with 1-ethyl-3-benyl-imidazolium bromide in DMSO at room temperature, and characterized by elemental analysis, 1H NMR and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P with a = 10.1597（10）, b =11.0646（11）, c = 13.0245（14） , α = 102.230（2）, β = 90.606, γ = 113.9250（10）o, V = 1300.3（2） 3, Mr = 748.06, Z = 2, Dc = 1.911 g/cm3, μ（MoKα） = 4.60 mm-1 and F（000） = 728. The structure was refined to R = 0.0316 and wR = 0.0835 for 3744 observed reflections with I 〉 2σ（I）. The title compound crystallizes as a centrosymmetric tetranuclear compound. One half of the molecule comprises the asymmetric unit of the structure. The Ag（1） atom is nearly linear or T-shaped when the Ag（1）-Ag（2） interaction is taken into consideration, which is bi-coordinated by two carbene carbon atoms. The Ag（2） atom adopts tetrahedral geometry. The catalytic behavior of the title complex has been investigated, and the results indicate it has a highly catalytic activation for L-lactide polymerization.
基金Supported by the Natural Science Foundation of Jilin Province (No. 20060516)the Doctoral Foundation of Jilin Normal University (No. 2006006 and No. 2007009)+1 种基金the Science and Technology Institute Foundation of Siping City (No. 2005016)the Subject and Base Construction Foundation of Jilin Normal University (No. 2006041)
文摘A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal gravimetry （TG）, fluorescent emission and single-crystal X-ray diffraction. Its crystal structure is of monoclinic, space group P2 1/c with a = 9.8897（8）, b = 14.2506（12）, c = 26.384（2） ,A, β = 94.8940（10）°, V = 3704.8（5） A3 Z = 2, C86H52N16O16S2Zn4, Mr = 1891.04, Dc = 1.695 g/cm^3, μ= 1.423 mm^-1, F（000） = 1920, GOOF = 1.039, the final R = 0.0358 and wR = 0.0872 for 6038 observed reflections with I 〉 2σ（I）. In 1, ＂cage-like＂ tetranuclear clusters of [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] are further stacked through π-π interactions to generate a 3D supramolecular network.
基金Supported by the National Natural Science Foundation of China(Nos. 20476011 and 20371007).
文摘The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.
基金supported by the Scientific Research Common Program of Beijing Municipal Commission of Education (No. KM201010028008)
文摘The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2·2H2O with 2-amino-1,3-thiazole in methanol and characterized by IR spectra and X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=9.7137（2）,b=10.7005（2）,c=14.6505（2）,α=83.9550（10）,β=82.0930（10）,γ=67.1640（10）°,V=1387.84（4）3,Mr=883.43,Z=2,μ=3.927 mm-1,Dc=2.1144 g/cm3,F（000）=868,R=0.0332 and wR=0.0814.The complex contains a tetrahedron of four CuII atoms coordinating to a central μ4-O atom,with the six edges of the tetrahedron bridged by six Cl atoms.The Cu-O bond distances range from 1.910（2） to 1.918（2）,Cu-Cl from 2.3501（11） to 2.5924（10）,and Cu-Cu from 3.1003（6） to 3.1663（6）.The coordination geometries of the four coppers distort from trigonal bipramid to tetragonal pyramid with different distortion factors.The free animo groups of the ligands result in a lot of N-H···Cl and N-H···N intra-and intermolecular hydrogen bonds.
基金Supported by the Key Laboratory of Environmental Engineering,Protection and Assessment of Guangxithe National Water Pollution Control and Management of China(No.2008ZX07317-02)the Startup Foundation for Dr.of Guilin University of Technology
文摘A novel tetranuclear nickel（II） complex [NiaL2（DMF）2（H20）2＇2DMF] （1, H4L = azo-enolic-2-hydroxybenzamide, DMF = N,N-dimethyl-formamide） has been synthesized and characterized by elemental analysis, UV, IR and X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P21/n with a = 8.8944（11）, b = 14.4583（18）, c = 18.097（2） A, fl = 90.00（2）, Z = 2 , V = 2327.2（5） A3, C40H48NI2Ni4OI4, Mr = 1155.66, Dc= 1.649 g/cm3,μ=1.672 mm1, F（000） = 1192, R = 0.0392 and wR = 0.0958. The local coordination environment around the nickel ions exist a distorted octahedral and quadrangle geometry in the molecular structure. Complex 1 exhibits strong photoluminescent emission in the ultraviolet region at room temperature. The electrochemical studies reveal that redox of Nia＋/Ni2＋ in the complex is a quasi-reversible process.
基金supported by the Foundation of State Key Laboratory of Coal Conversion(No.J17-18-611)the National Natural Science Foundation of China(No.21676258)
文摘Two novel zinc（Ⅱ） coordination polymers, [Zn2（BCB）（CH3OH）（μ3-OH）]n（1） and {[Zn2（BCB）（μ3-OH）（H2O）2]·CH3OH}n （2）, have been constructed from 3,5-bis（2-carboxylphenoxy）benzoic acid（H3BCB） and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. Structural analysis reveals that complexes 1 and 2 are both 1D polymeric chains with unprecedented tetranuclear {Zn4（COO）4（μ3-OH）2} clusters, which were further expanded into a 2D structure. Fluorescence measurements show that 1 and 2 have highly selective and sensitive detection of nitrobenzene.
基金This project was supported by the National Natural Science Foundation of China (No. 20331010) and Natural Science Foundation of Tianjing (No. 033602011)
文摘A novel oxamide-bridged trimeric tetranuclear complex 1 incorporating a macro- cyclic oxamide of formula {[(CuL)3Mn](ClO4)2}3 (macrocyclic oxamide L = 2,3-dioxo-5,6,14,15- dibenzo-1,4,8,12-tetraazacyclopentadeca-7,12-diene) was prepared and structurally characterized. The compound [(CuL)3Mn](ClO4)2 crystallizes in the trigonal system, space group P 3 with a = 22.434(17), b = 22.434(17), c = 18.82(2) ?, α = β = 90, γ = 120o, V = 8203(13) ?3, Z = 6, Dc = 1.751g/cm3, μ(MoKα) = 1.557, F(000) = 4392, the final R = 0.083 and wR = 0.1727 for 9604 obser- ved reflections with I > 2σ(I). The single-crystal X-ray analysis shows that 1 is a trimeric complex. There are three similar constitutes, dissimilar conformations and asymmetrically independent ‘building-block’ [(CuL)3Mn] in one crystal cell of the title complex 1.
基金Supported by the National Key Project of Fundamental Research and the National Natural Science Foundation ofChina(No.29771001,
文摘The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.
基金Supported by the National Key Project of Fundamental Research and the National Natural Science Foundation ofChina(No.29771001,
文摘The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.
基金The project supported by the National Natural Science Foundation of China
文摘The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central μ_4-O atom and the four Nd atoms.The results of calculation show that the μ_4-O atom uses its sp^3 valence orbitals to contribute four O-Nd bonding MOs with character of multicenter bond apparent- ly.The Mulliken population analysis shows that the overlap population between Nd atoms is almost equal to zero,therefore there is no direct metal-metal bond between Nd atoms.The coordination number of Nd in the complex is discussed briefly.
基金supported by the NNSFC(No.20871023)the Jilin Provincial Science Research Foundation of China(No.20101549)+1 种基金Xiaonei Foundation of Changchun University of TechnologyThe 12th Five-Year Plan for Science&Technology Research sponsored by Department of Education of Jilin Province(Nos.130 and 146,2013)
文摘A unique metal-organic framework [Cd2（L）1.5（μ3-OH）（H2 O）2 ]·2H2 O（1, H2 L = 2,5-dibenzoylterephthalic acid） has been synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffractions, elemental analyses, IR spectra and fluorescence spectrum. The compound is of triclinic system, space group P1, C33 H27 CdO14, Mr = 870.33, a = 12.2939（17）, b = 12.5135（9）, c = 13.2046（10）, α = 115.3190（10）, β = 96.9140（10）, γ = 109.7950（10）°, V = 1641.6（3）3, Z = 2, Dc = 1.761 g/cm3, F（000） = 862, μ（MoK） = 1.366 mm-1, Rint = 0.0148, R = 0.0240 and wR = 0.0639 for 5995 observed reflections with I 〉 2σ（I）. X-ray analysis shows that the title complex exhibits a 3D framework with（412·63） topology, in which the tetra-nuclear [Cd4（μ3-OH）2 ] clusters act as 6-connected nodes, and the L ligands can be simplified to be linear connectors. Moreover, the thermal stability and fluorescence have been studied in detail.
基金Supported by the National Natural Science Foundation of China(No.21372051,61671162)the Science and Technology Planning Project of Guangdong Province(No.2013B021700001,2016A010103031)+1 种基金the Excellent Young Teacher Development Project of Universities in Guangdong Province(No.261532106)the Guangzhou Science and Technology Program(No.502150105)
文摘One novel Co（II） coordination polymer, namely [Co4（L）6（NO3）2] （1） was prepared by solvothermal reactions of Co（NO3）2 with a （E）-2-[2-（3-thienyl）ethenyl]-8-quinolinol ligand （HL）, which has been determined by single-crystal X-ray diffraction analyses and further characterized by means of elemental analyses, IR spectra, PXRD and thermogravimetric analyses （TGA）. The core structure of complex 1 is an incomplete dicubane-like tetranuclear Co（II） cluster, which is surrounded by six 8-hydroxy-quinolinate-based ligands and two nitrate ligands. Weak S-O interactions between the thienyl groups and nitrate ligands extend the adjacent tetranuclear CoOI） clusters into a supramolecular （4, 4） net structure. Magnetic measurement indicates that the coupling within both molecules is overall antiferromagnetic.
基金Supported by the key Foundation of the Education Department of Hubei Province (No. D20081503)the foundation of the innovative group of the Education Department of Hubei Province (T200802)
文摘The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.
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.
基金Supported by the National Natural Science Foun-dation of China(20471044)
文摘A tetranuclear zinc benzoate Zn_(4)O(C6H5CO_(2))6 was synthesized and characterized by X-ray single crystal determination.It crystallizes in cubic,space groupIa-3d.Its crystal cell is very large,a=4.10063(18)nm,V=68.953(5)nm3 and Z=48.The structure is composed of discrete Zn_(4)O(C6H5CO_(2))6 molecules.In each molecule,four zinc atoms are held together by a central oxygen atom,which results in the formation of a regular tetrahedron.All benzoate ligands coordinate to zinc atoms in a bidentate bridging mode.Each zinc atom is in a slightly distorted tetrahedral geometry,coordinated by three benzoate oxygen atoms and the central oxygen atom.The intermolecular interactions result in the formation of a three-dimensional supramolecular framework,with non-intersecting parallel channels.
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The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in the presence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c, Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4; Dc=1.78g/cm^3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]cluster core and t-(dtp)^(-1)ligands are retained and only μ-bridged(dtp)^(-1)ligands are substituted by(C_6H_5CO_2)^(-1)in the substitution reaction,thus producing the new title cluster compound,the structure of which contains two species of bidentate ligand.
文摘A new tetranuclear silver（I） complex with the formula of [Ag4（MMPzA）2（dmPz）4（H2DPC）2]（H2O）4（1, MMPz A = mono（3,5-bimethyl-pyrazolmethyl）amine）, dm Pz = 3,5-dimethylpyrazole, H2DPC = pyridine-3,4-dicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction method. The title complex crystallizes in the triclinic system, space group P1 with a = 10.5532（13）, b = 11.5071（18）, c = 13.3951（17） A, α = 97.3190（10）, β = 106.7360（10）, γ = 108.0770（10）o, V = 1438.3（3） A3, Z = 1, Dc = 1.691 g/cm3, F（000） = 736, μ = 1.421 mm-1, the final R = 0.0400 and w R = 0.0942 for 5097 observed reflections（I 〉 2σ（I））. The intermolecular hydrogen bonding interaction extends the complex into a 1D chain structure. In addition, the complex was tested in vitro for its antibacterial activity and it exhibited significant activity, especially against penicillium.
文摘In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine), are synthesized from the reaction of well characterized Lewis base [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>O<sub>2</sub>] with carbon dioxide as a Lewis acid in CH<sub>2</sub>Cl<sub>2</sub>. These carbonato-derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH<sub>2</sub>Cl<sub>2</sub>or phNO<sub>2</sub>. Cryoscopic measurements support tetranuclear structure for all of them. Electronic spectra in the near infrared with high molecular absorptivity may be explained for tetranuclear cuban structure to fulfil 3 halo-ligands for each copper centre in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>]. The EPR spectra for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] complexes are axial type of spectra (d<sub>x2-y2</sub> G.S) suggesting elongated tetragonal distortion for all of them. Cyclic voltammograms for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] are irreversible in character. These tetranuclear carbonato complexes show catalytical activity. They initiate the oxidation of 2,6-dimethylphenol (DMP) to 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ).
文摘Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.
