A nonanuclear copper(II) polyoxometalate assembled around a μ-1,1,1,3,3,3-azido ligand and its parent tetranuclear complex

被引:163
作者
Mialane, P
Dolbecq, A
Marrot, J
Rivière, E
Sécheresse, F
机构
[1] Univ Versailles, IREM, UMR 8637, Inst Lavoisier, F-78035 Versailles, France
[2] Inst Chim Mol & Mat Orsay, UMR 8613, Chim Inorgan Lab, F-91405 Orsay, France
关键词
azides; copper; magnetic properties; polyoxometalates; tungsten;
D O I
10.1002/chem.200400769
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Reaction of Cu-II, [gamma-SiW10O36](8-), and N-3(-) affords three azido polyoxotungstate complexes. Two of them have been characterized by single-crystal X-ray diffraction. Complex KNaCs10[{gamma-SiW10O36Cu2(H2O)(N-3)(2)}(2)](.)26H(2)O (1) is obtained as crystals in few hours after addition of CsCl. This linear tetranuclear Cu-II complex consists in two [gamma-SiW10O36Cu2(H2O)(N-3)(2)](6-) units connected through two W=O bridges. When the filtrate is left to stand for one night, a new complex is obtained. From both elemental analysis and IR spectroscopy, it has been postulated that this compound could be formulated K15Cs5.5[SiW10O37Cu2(H2O)(2)(N-3)](.)14H(2)O (1a), showing the loss of one azido ligand per polyoxometalate unit. Finally, when no cesium salt is added to the reaction medium, the nonanuclear complex K12Na7[{SiW8O31Cu3(OH)(H2O)(2)(N-3)}(3)(N-3)](.)24H(2)O (2) is obtained after three days. Compound 2 crystallizes in the R3c space group and consists in three {Cu-3} units related by a C-3 axis passing through the exceptional mu-1,1,1,3,3,3-azido bridging ligand. Each trinuclear Cu-II unit is embedded in the [gamma-SiW8O31](10-) ligand, an unprecedented tetravacant polyoxometalate, showing that partial decomposition of the [gamma-SiW10O36](8-) precursor occurs with time in such experimental conditions. Magnetically, complex 1 behaves as two isolated {Cu-2(mu(1.1)-N-3)(2)} pairs in which the metal centers are strongly ferromagnetically coupled (J=+224 cm(-1), g=2.20), the coupling through the W=O bridges being negligible. The magnetic behavior of complex 2 has also been studied. Relatively weak ferromagnetic couplings (J(1) = +1.0 cm(-1), J(2) = + 20.0 cm(-1), g = 2.17) have been found inside the {Cu-3} units, while the intertrimeric magnetic interactions occurring through the hexadentate azido ligand have been found to be antiferromagnetic (J(3) = -5.4 cm(-1)) and ferromagnetic (J(4) = + 1.3 cm(-1)) with respect to the end-to-end and end-on azido-bridged Cu-II pairs, respectively.
引用
收藏
页码:1771 / 1778
页数:8
相关论文
共 41 条
  • [1] ANDERSON TF, COMMUNICATION
  • [2] CRYSTAL AND MOLECULAR-STRUCTURES OF DI-MU-AZIDO-BIS-[N,N,N',N'-TETRAMETHYLETHYLENEDIAMINE AZIDO COPPER(II)]
    BKOUCHEWAKSMAN, I
    SIKORAV, S
    KAHN, O
    [J]. JOURNAL OF CRYSTALLOGRAPHIC AND SPECTROSCOPIC RESEARCH, 1983, 13 (04): : 303 - 310
  • [3] High-nuclearity magnetic clusters:: Generalized spin Hamiltonian and its use for the calculation of the energy levels, bulk magnetic properties, and inelastic neutron scattering spectra
    Borrás-Almenar, JJ
    Clemente-Juan, JM
    Coronado, E
    Tsukerblat, BS
    [J]. INORGANIC CHEMISTRY, 1999, 38 (26) : 6081 - 6088
  • [4] MAGPACK1 a package to calculate the energy levels, bulk magnetic properties, and inelastic neutron scattering spectra of high nuclearity spin clusters
    Borrás-Almenar, JJ
    Clemente-Juan, JM
    Coronado, E
    Tsukerblat, BS
    [J]. JOURNAL OF COMPUTATIONAL CHEMISTRY, 2001, 22 (09) : 985 - 991
  • [5] A new heptanuclear cobalt(II) cluster encapsulated in a novel heteropolyoxometalate topology:: Synthesis, structure, and magnetic properties of [CO7(H2O)2(OH)2P2W25O94]16-
    Clemente-Juan, JM
    Coronado, E
    Forment-Aliaga, A
    Galán-Mascarós, JR
    Giménez-Saiz, C
    Gómez-García, CJ
    [J]. INORGANIC CHEMISTRY, 2004, 43 (08) : 2689 - 2694
  • [6] Magnetic clusters from polyoxometalate complexes
    Clemente-Juan, JM
    Coronado, E
    [J]. COORDINATION CHEMISTRY REVIEWS, 1999, 193-5 : 361 - 394
  • [7] DINUCLEAR COPPER(II) CRYPTATES OF MACROCYCLIC LIGANDS - SYNTHESIS, CRYSTAL-STRUCTURE, AND MAGNETIC-PROPERTIES - MECHANISM OF THE EXCHANGE INTERACTION THROUGH BRIDGING AZIDO LIGANDS
    COMARMOND, J
    PLUMERE, P
    LEHN, JM
    AGNUS, Y
    LOUIS, R
    WEISS, R
    KAHN, O
    MORGENSTERNBADARAU, I
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (23) : 6330 - 6340
  • [8] Alternating ferromagnetic-antiferromagnetic interactions in a manganese(II)-azido one-dimensional compound: [Mn(bipy)(N-3)(2)]
    Cortes, R
    Drillon, M
    Solans, X
    Lezama, L
    Rojo, T
    [J]. INORGANIC CHEMISTRY, 1997, 36 (04) : 677 - 683
  • [9] 2 NEW MU-AZIDO NICKEL(II) UNIFORM CHAINS - SYNTHESES, STRUCTURES, AND MAGNETOSTRUCTURAL CORRELATIONS
    ESCUER, A
    VICENTE, R
    RIBAS, J
    ELFALLAH, MS
    SOLANS, X
    FONTBARDIA, M
    [J]. INORGANIC CHEMISTRY, 1993, 32 (17) : 3727 - 3732
  • [10] Structure and magnetic behaviour of the first singly bridged nickel cyanate chain and a new dinuclear complex: An approximation to the superexchange mechanism for the nickel pseudohalide system
    Escuer, A
    Vicente, R
    ElFallah, MS
    Solans, X
    FontBardia, M
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (06): : 1013 - 1019