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1.
The reaction of α-H3[PW12O40] with Y(NO3)3 in the presence of DMF or DMSO leads to two complexes with the formulae {Y(DMSO)7}·PW12O40(1) and {[Y(DMF)7]2PW12O40}·PW12O40(2). The crystal structures indicate that complex 1 consists of discrete [YLn]3+ cations and α-Keggin heteropolyanions [PW12O40]3-, whereas, in complex 2, donor-acceptor interaction results in a cation-anion-cation triplet. In addition, the electrochemical behavior of the two complexes indicates the usual successive reduction processes of the W atoms in the anions.  相似文献   

2.
Two dinuclear lanthanide (Ln) complexes, formulated as [phen2Ln2(HCOO)4(HCOO)2-2x(NO3)2x](1, Ln=Gd and x=0.52; 2, Ln = Er and x = 0.90; phen = 1,10-phenanthroline), were synthesized and characterized. They are isostructural. The dinuclear molecule consists of two Ln 3+ bridged by four formate groups and chelated by phen and formate/nitrate ligands, and the Ln 3+ possesses a coordination environment of distorted tri-capped trigonal prism of LnO 7 N 2 . Both compounds behave as paramagnets between 2 and 300 K, but display two static field induced magnetic relaxation processes. One is slow and of spin-lattice type, and it results from the lifting of Kramer’s degeneracy of the ground-states of both Gd 3+ and Er 3+ , and the other is fast, and it might be spin-spin type.  相似文献   

3.
Six novel u-oxamido binuclear complexes, namely Cu(oxpn)Ln(L)2(ClO4)3 (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro-1,10-phenanthroline (abbreviated as NO2-phen), have been synthesized and characterized. The magnetic susceptibility of complexes Cu(oxpn)Gd(NO2-phen)2(ClO4)3.2H2O was measured over the 4-300 K and the observed data were successfully simulated by equation based on spin Hamil-tonian operator (H = -2JS1.S2), giving the exchange integral J(Cu-Gd)=-1.62 cm-1. This indicates a weak antiferromagnetic interaction between the Cu(Ⅱ) and Gd(Ⅲ) ions.  相似文献   

4.
Ti+(CO2)2Ar and Ti+(CO2)n (n=3-7) complexes are produced by laser vaporization in a pulsed supersonic expansion. The ion complexes of interest are each mass-selected in a time- of-flight spectrometer, and studied with infrared photodissociation spectroscopy. For each complex, a sharp band in the CO stretching frequency region is observed, which confirms the formation of the OTi+CO(CO2)~_l oxide-carbonyl species. Small OTi+CO(CO2)~_1 complexes (n_〈5) exhibit CO stretching and antisymmetric CO2 stretching vibrational bands that are blue-shifted from those of free CO and CO2. The experimental observations indicate that the coordination number of CO and CO2 molecules around TiO+ is five. Evidence is also observed for the presence of another electrostatic bonding Ti+(CO2)2 structural isomer for the Ti+(CO2)2Ar complex, which is characterized to have a bent OCO-Ti+-OCO structure stabilized by argon coordination.  相似文献   

5.
Two novel complexes {[Co(A-glu)(Im)2]·0.5H2O}n (1) and [Cd(A-glu)(Im)3]n (2) (H2A-glu=N-acetyl-L-glutamic acid, Im=imidazole) have been synthesized from the reaction of H2A-glu with Co(CH3COO)2·4H2O or Cd(CH3COO)2·2H2O in the presence of Im. Both of the complexes display different coordination environment and similar one-dimensional chain structure. The magnetic susceptibility measurements for 1 show a weak antiferromagnetic interaction between two cobalt(Ⅱ) ions bridged by A-glu ligand. The complex 2 exhibits an intense fluorescent emission in solid state at room temperature.  相似文献   

6.
Two new bimetallic cyano-bridged complexes [Ln(DMSO)2(H2O)(μ-CN)4Fe(CN)2] (Ln = Ce 1, Eu 2) have been prepared by the grinding reaction method and structurally characterized by X-ray single-crystal structure analysis. Crystallographic data for 1: C10H14CeFeN6O3S2, Mr = 526.36, monoclinic, P2/n, a = 7.852(4), b = 10.729(5), c = 11.181(5)A,β = 96.992(8)°, V = 935.0(7) A^3, Z = 2, Dc = 1.870 g/cm^3,/1 = 3.421 mm^-1, F(000) = 512, R = 0.0363 and wR = 0.0971; and those for 2: C10H14EuFeN6O3S2, Mr = 538.20, monoclinic, P21n, a = 7.739(5), b = 10.668(7), c = 11.008(7) A,β = 96.943(3)°, V = 902.1(11) A^3, Z = 2, Dc = 1.981 g/cm^3,/1 = 4.499 mm^-1, F(000) = 522, R = 0.0345 and wR = 0.0855. In each complex the lanthanide ion is seven-coordinated in a pentagonal bipyramidal arrangement, and the Fe(Ⅲ) ion is in a nearly regular octahedral environment. The title complexes can be described as two- dimensional (2-D) stair-like structures, which are further connected by hydrogen bonds to form three-dimensional (3-D) frameworks.  相似文献   

7.
The magnetic property of u3-oxotriiron(III) complex [Fe3O(OBz)6(CH3OH)3](NO3)-(CH3OH)2 (HOBz=benzoic acid) has been studied. We use isosceles triangle model and molecular field correction to fit the experimental magnetic susceptibility data. It shows that an intramolecular antiferromagnetic exchange interaction occurs with J=-31.27 cm-1, J'=-27.26 cm-1, and a weaker intermolecular antiferromagnetic exchange interaction occurs with zJ'=-3.76 cm-1. We give the d5-d5-d5 energy level diagram of triiron(III) complex as a function of J'/J. From the diagram we can get the total spin ST of the complex as 1/2 in the ground state.  相似文献   

8.
Reactions of NiCl2-6H2O with dmpzm and formic or acetic acid at PH = 7 produced the two title compounds, [Ni(dmpzm)2(HCO2)]Cl·2H2O 1 and [Ni(dmpzm)2(OAc)]C2·H2O 2 (dmpzm = 1,1 '-methylenebis(3,5-dimethyl-lH-pyrazole)). 1 and 2 were characterized by elemental analysis, IR spectra, and thermogravimetric analysis. 1 crystallizes in the orthorhombic system, space group Pcca with a = 18.700(2), b = 8.6843(9), c = 18.098(2)A, V= 2939.1(5)A^3, Z = 4, Dc = 1.319 g/cm^3, T = 193 K, C23H37CINsNiO4, Mr = 583.75, F(000) = 1232, p(MoKa) = 0.792 cm^-1, S = 1.079, R = 0.0772 and wR = 0.1958 for 2265 observed reflections with I〉 2σ(I). 2 crystallizes in the orthorhombic system, space group Pcca with a = 17.011(3), b = 18.630(4), c = 19.300(4)A, V = 6117(2)A^3, Z = 8, Dc = 1.337 g/cm^3, T= 193(2) K, C24H41C1N8NiO5, Mr = 615.79, F(000) = 2608, μ(MoKa) = 0.768 cm^-1, S = 1.059, R = 0.0518 and wR = 0.1109 for 5124 observed reflections with I 〉 2σ(I). The Ni atoms in 1 or 2 are chelated by two dmpzm ligands and one formate or acetate anion, forming slightly distorted octahedral geometries. In the crystals of 1 or 2, intermolecular hydrogen bonding interactions result in the formation of 2D hydrogen-bonded frameworks.  相似文献   

9.
In order to study the Fe-Cu interactions and their effects on 31p NMR, the structures of mononuclear complex Fe(CO)3fPhzPpy)a 1 and binuclear complexes Fe(CO)3(PhEPpy)z(CuXn) (2: Xn = Cl2^2-, 3: Xn = Cl-, 4: Xn = Br-) are calculated by density functional theory (DFT) PBE0 method. For complexes 1, 3 and 4, the 31p NMR chemical shifts calculated by PBE0-GIAO method are in good agreement with experimental results. The 31p chemical shift is 82.10 ppm in the designed complex 2. The Fe-Cu interactions (including Fe→Cu and Fe←Cu charge transfer) mainly exhibit the indirect interactions. Moreover, the Fe-Cu(I) interactions (mostly acting as σFe-p→4Scu and aFe-C→4Scu charge transfer) in complexes 3 and 4 are stronger than Fe-Cu(Ⅱ) interactions (mostly acting as σFe-p→4Scu and σFe-p←4Sc,) in complex 2. In complex 2, the stronger Fe←Cu interac- tions, acting as σFe-p←44SCu charge transfer, increase the electron density on P nucleus, which causes the upfield 31p chemical shift compared with mononuclear complex 1. For 3 and 4, although a little deshielding for P nucleus is derived from the delocalization of σFe-p→4Scu due to the Fe→Cu interactions, the stronger σFe-c→np charge-transfer finally increases the electron density on P nucleus. As a result, an upfield 31p chemical shift is observed compared with 1. The stability follows the order of 2〉3=4, indicating that Fe(CO)3(PhzPpy)2(CuCl2) is stable and could be synthesized experimentally. The N-Cu(Ⅱ) interaction plays an important role in the stability of 2. Because the delocalization of σFe-p→4SCu and σFe-c→πc-o weakens the a bonds of Fe-C and ~r bonds of CO, it is favorable for increasing the catalytic activity of binuclear complexes. Complexes 3 and 4 are expected to show higher catalytic activity compared to 2.  相似文献   

10.
(C5H4SiMe2^tBu)2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [(C5H4SiMe2^tBu)2Ln(μ-S^nBu)]2 (Ln = Y (1), Er (2)). Complexes 1 and 2 have been characterized by elemental analysis, IR, mass spectroscopy and X-ray single-crystal diffraction analysis. Both complexes are of monoclinic with space group P21/c, formula C52H94S2Si4Y2 1 (C52H94S2Si4Er2 2) Mr = 1073.57 (1230.27), a = 8.495(2) (8.41(2)), b = 26.913(8) (26.67(7)), c = 13.756(4) (13.68(4)) A, α = 90(90), β = 101.184(5) (101.57(4)), γ = 90 (90)°, V= 3085.1(15) (3007(14)) A^3, Dc = 1.156 (1.359) g·cm^-3, Z= 2 (2), F(000) = 1144 (1260), μ = 2.046 (2.951) cm^-1, R = 0.0687 (0.0749) and wR = 0.1306 (0.1507) for observed reflections with I 〉 2σ(I). X-ray structures of 1 and 2 definitively prove that only one sulfur atom is inserted into the Ln-C(^nBu) bond, forming a thiolate ligand.  相似文献   

11.
Five novel complexes of formula [Ln(hfac)3] · BNPhOM, where Ln = Gd, Ho, Dy, Y, Er; hfac = hexfluoracetylaceto-nate; BNPhOM = 1,3-[bis-2,2'-(4,4,5,5-tetramethyl-4,5-di-hydro-1H-imidazolyl-1-oxyl-3-oxide)phenoxy] propane, have been prepared and characterized by elemental analysis, molar conductances, IK and electronic spectra. The temperature dependence of the magnetic susceptibility for Gd( III) and radical was measured (2-300 K). The observed data were successfully simulated giving the exchange integral J = 0.28 cm-1, J' = - 0.33 cm-1. These results indicate a weak ferromagnetic spin exchange interaction between Gd(III) ion and the radical and a weak antiferromagnetic spin exchange interaction between the radical and radical.  相似文献   

12.
赵丹  郑寿添  杨国昱 《结构化学》2009,28(4):503-508
One new arsenic-vanadium cluster, [Zn(dien)(Hdien)]2[As6V15O42(H2O)]·4H2O (1, dien = diethylenetriamine), has been hydrothermally synthesized and characterized by IR, elemental analysis, TGA, magnetic property and single-crystal X-ray diffraction analysis. Crystal data for 1: monoclinic, space group P21/n, a = 13.959(3), b = 22.428(5), c = 22.831(5) A^°, β = 90.733(4)°, Z = 4. X-ray crystallographic study showed that compound 1 is constructed from [As6V15O42(H2O)]^6- polyoxoanions linked together by novel [Zn(dien)(Hdien)]^3+ complex fragments via hydrogen bonds into a three-dimensional network. Variable temperature susceptibility measurement demonstrates the presence of antiferromagnetic interaction between V^IV cations in 1.  相似文献   

13.
The reactions of dilithium salt of trans-1,2-bis(trimethylsilylamino)cyclohexane with anhydrous lanthanide trichlorides LnCl3 (Ln = Yb, Nd) in THF afforded the dianionic binuclear tricycles of lanthanide chlorides {Li(THF)3[LnCl(μ2-trans-1,2-(NSiMe3)2C6H10)(μ2-Cl)]}2·2THF (Ln=Yb 1, Nd 2) in moderate yields. Both of the bridged complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that the two complexes are the analogues which have a tricyclic framework built by two bridged lanthanide metals, four nitrogens and four carbons from two diamide ligands. Each lanthanide metal coordinates to three nitrogen atoms and two chlorines to form a distorted trigonal bipyramid and connects with a lithium by a bridging chlorine.  相似文献   

14.
A three-dimensional Cu^2+ supramolecular complex [Na2Cu(BTA)2(H2O)8]·H2O 1 (H2BTA = bistetrazolylamine) was synthesized by reacting the aqueous solution of CuSO4·5H2O and H2BTA under stirring. The crystal structure of 1 was determined by single-crystal X-ray diffraction. The result indicates that 1 crystallizes in triclinic, space group P1, with a = 7.0518(2), b = 12.2692(2), c = 13.8583(3) A, α = 115.7260(10),β = 93.2440(10), γ = 98.3610(10)°, Mr = 573.90, V= 1059.01(4) A^3, Z = 2, De= 1.800 g·cm^-3,μ(MoKα) = 1.155 mm^-l, F(000) = 586.0, S = 1.074, the final R = 0.0273 and wR = 0.0744 for 4334 observed reflections with I 〉 2σ(I). The Cu^2+ ion is five-coordinated with a N4O1 donor set with r = 0.153 according to the method of Addison et al. And the Na^+ ions form an infinite main chain through bridging O atoms from coordinated water molecules. In 1, a three-dimensional supratnolecular network is formed by O-H….O, O-H…N, N-H…O and N-H…N hydrogen bonds.  相似文献   

15.
Three homoleptic lanthanide complexes, [C6H5COCHC(CH3)N(p-CIC6H4)]3Ln(THF)n (n = 0, Ln = Yb (1); n = 0, Ln = Y (2); n = 1, Ln = Nd (3)), were synthesized by amine elimination reaction of Ln[N(SiMe3)2]3 with 1-phenyl-3-N-(p-chlorophenylimino)-1-butanone. These com- plexes crystallize in triclinic, space group PI with a = 9.805(3), b = 14.831(6), c = 16.075(6) A, a = 111.996(9), β = 91.570(7), y = 93.744(6)° V= 2159.4(13) A3, Z= 2, Dc = 1.515 g/cm3, F(000) = 986, μ(MoKa) = 2.396 mm-1, R = 0.0360 and wR = 0.0850 for 9548 observed reflections with I 〉 20(I) for complex 1; a = 9.861(5), b = 14.852(9), c = 16.111(9) A, a = 112.362(13),β = 91.949(11), y = 93.678(14)°, V= 2173(2) A3, Z= 2, Dc = 1.377 g/cm3, F(000) = 924,μ(MoKa) = 1.570 mm-1, R = 0.0735 and wR = 0.1389 for 8015 observed reflections with I 〉 20(I) for complex 2; and a = 9.308(3), b = 15.357(3), c = 17.419(4) A, a = 66.493(13), β = 88.61(2), y = 86.664(19)°, V = 2279.4(9) A3, Z= 2, Dc = 1.499 g/cm3, F(000) = 1046,μ(MoKa) = 1.364 mm-1, R = 0.0843 and wR = 0.2280 for 8433 observed reflections with I 〉 20(I) for complex 3. Each central metal in complexes 1 and 2 is six-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands to give a distorted octahedral geometry, while the central metal in 3 is seven-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands and one oxygen atom from the solvated THF molecule to complete a distorted monocapped trigonal prism.  相似文献   

16.
A series of 1D nickel(Ⅱ)/zinc(Ⅱ)-lanthanide(Ⅲ) coordination polymers, [M(μ-L)2Ln(NO3)3]n· solvents (HL =bis(2-pyridylcarbonyl)amine; M = Ni, Ln = Gd (1 · NiGd), Tb (2· NiTb), Dy (3· NiDy), Ho (4· NiHo), Y (5· NiY);M = Zn, Ln =Gd (6· ZnGd), Tb (7· ZnTb), Dy (8· ZnDy), Ho (9· ZnHo); solvents = H2O or H2O-ethanol), was synthesized and characterized. All of the complexes are isostructural at 293 K and crystallize in the orthorhombic space group Fddd. Magnetic measurements were performed on 1-9, where weak ferromagnetic interaction is found in 1 · NiGd, ferromagnetic interaction in 2·NiTb and 3·NiDy, and antiferromagnetic interaction in 4· NiHo. A remarkable dc magnetic field dependence of ac susceptibilities was found in this series of complexes.  相似文献   

17.
The title complex, [Mn(DPPZ)(PZDC)(H2O)] 1 (DPPZ = dipyrido[3,2 -a:2',3'- c]phenazine and H2PZDC = pyrazine-2,3-dicarboxylic acid), has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analyses, IR, TG- DTA and magnetic susceptibility measurement. It crystallizes in triclinic, space group P1^- with a = 6.6842(5), b = 7.5741(6), c = 20.5755(15)A, α = 90.1160(10), β = 97.0560(10), γ = 97.3350(10)°, V= 1025.16(13)A^3, Z = 2, MnC24H14N6O5, Mr= 521.35, Dc= 1.689 g/cm^3, F(000) = 530, μ(MoKa) = 0.699 mm^-1, R = 0.0366 and wR = 0.0810. Compound 1 contains one- dimensional chains which are further stacked through π-π interactions to form a 3D supramolecular architecture. The water molecule O(1W) is involved in hydrogen bonding interactions with symmetric carboxylate oxygen atom 0(4) at (x+ 1, y+1, z) and symmetric PZDC nitrogen atom N(6) at (1-x, 1-y, 1-z), which completes the structure of 1. Magnetic susceptibility measurement indicates that the compound behaves a weak antiferromagnetic exchange interaction.  相似文献   

18.
Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni2(Bpy)3(Dto)2(H2O)3(1), Ni2(Phen)3(Dto)2(H2O)3(2) and Ni2(Me2Bpy)3(Dto)2(H2O)2 (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline, Me2Bpy=4,4′-dimethyl-2,2′-bipyridine, Dto2-=Dithiooxalate), and characterized by elemental analyses, IR, UV-Visible spectra, conductance. The variable temperature magnetic susceptibilities for the complexes were measured in the range of temperature between 1.5 K and 298 K. Experimental data of magnetic susceptibility were successfully fit to theoretical value based on the spin Hamiltonian operator:(?), S1=S2=1, giving the magnetic exchange parameters of 2J=-52.8 cm-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions. The magnetic exchange parameters of the binuclear Nickel(Ⅱ) complexes bridged with dithiooxalate is larger than that of the binuclear Nickel(Ⅱ) complexes bridged with oxalate. Dithiooxalate is more effective to transfer antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions than oxalate.  相似文献   

19.
A series of 1D nickel(II)/zinc(II)-lanthanide(III) coordination polymers, [M(μ-L)2Ln(NO3)3]n·solvents (HL = bis(2-pyridylcarbonyl)amine; M = Ni, Ln = Gd (1·NiGd), Tb (2·NiTb), Dy (3·NiDy), Ho (4·NiHo), Y (5·NiY); M = Zn, Ln = Gd (6·ZnGd), Tb (7·ZnTb), Dy (8·ZnDy), Ho (9·ZnHo); solvents = H2O or H2O-ethanol), was synthesized and characterized. All of the complexes are isostructural at 293 K and crystallize in the orthorhombic space group Fddd. Magnetic measurements were performed on 1―9, where weak ferromagnetic interaction is found in 1·NiGd, ferromagnetic interaction in 2·NiTb and 3·NiDy, and antiferromagnetic interaction in 4·NiHo. A remarkable dc magnetic field dependence of ac susceptibilities was found in this series of complexes.  相似文献   

20.
蔡成翔  何坤欢  蒋毅民 《结构化学》2009,28(10):1275-1280
The title complex [Cu2(Sams)2(H2O)2(bipy)]·(H2O) 1 (H2Sams = N-(2-hydroxybenzy) aminomethanesulfonic acid, bipy = 4,4′-bipyridine) has been synthesized by the reaction of Cu- (CH3COO)2·H2O, nESams and 4,4′-bipyridine in aqueous methanol. It was characterized by IR, elemental analysis, thermogravimetric analysis (TGA) and X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group P21/n with a= 10.9533(17), b = 8.3408(13), c = 16.714(3) A^°, β = 101.295(4)°, V = 1494.3(4) A^°3 and Z = 2. The asymmetric unit is comprised of a tridentate Schiff base Sams^2- anionic ligand, a 4,4′-bipyddine and two coordinated water molecules, thus forming a binuclear copper(Ⅱ) complex. The coordination environment at Cu^Ⅱ center is described as a slightly distorted square pyramidal geometry. Via intermolecular hydrogen bonds C(10)-H(10)…O(3) and C(13)- H(13)…O(3), an infinite supramolecular chain is yielded. A number of intermolecular hydrogen bonds greatly contribute to the stabilization of the solid-state structure for 1.  相似文献   

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