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Synthesis, Structures, and Magnetic Properties of Heteronuclear Cu(II)−Ln(III) (Ln = La, Gd, or Tb) Complexes
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    Synthesis, Structures, and Magnetic Properties of Heteronuclear Cu(II)−Ln(III) (Ln = La, Gd, or Tb) Complexes
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    State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, and School of Pharmaceutical Science, Sun Yat-Sen University, Guangzhou 510275, P. R. China
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2005, 44, 23, 8285–8292
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    https://doi.org/10.1021/ic0507159
    Published October 11, 2005
    Copyright © 2005 American Chemical Society

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    Facile one-pot reactions led to the formations of dinuclear [CuLn(hmp)2(NO3)3(H2O)2] (Ln = Tb (1·Tb), Gd (1·Gd), or La (1·La)), and trinuclear [Cu2Ln(mmi)4(NO3)(H2O)2](ClO4)(NO3)·2H2O (Ln = Tb (2·Tb) or Gd (2·Gd)) and [Cu2La(mmi)4(NO3)2(H2O)](ClO4)·2H2O (2·La) with polydentate ligands 2-(hydroxymethyl)-pyridine and 2-hydroxymethyl-1-methyl-imidazole. In these complexes, each pair of Cu(II) and Ln(III) ions is linked by a double μ-alkoxo bridge. The temperature dependences of the magnetic susceptibilities of 1 and 2 were investigated in the range of 2−300 K. The dinuclear and trinuclear Cu−Gd complexes exhibit ferromagnetic interaction. The coupling constant J values in the heterodinuclear Cu−Gd complexes are correlated to values of the dihedral angles α between the two O−Cu−O and O−Gd−O fragments of the bridging CuO2Gd networks, with the largest J value associated with the smallest α value. The occurrence of a ferromagnetic interaction between CuII and GdIII ions of the trinuclear entity is supported by the field dependence of the magnetization. The field dependence of the magnetization at 2 K of 1·Gd and 2·Gd confirms the nature of the ground state and of the CuII−GdIII interaction, while alternating current susceptibility measurements demonstrates out-of-phase ac susceptibility signals of 1·Tb, which is the molecule-based magnetic material of the smallest nuclearity which exhibits frequency-dependent behavior within the 3d−4f mixed-metal systems.

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     School of Chemistry and Chemical Engineering.

     School of Pharmaceutical Science.

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    Cite this: Inorg. Chem. 2005, 44, 23, 8285–8292
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    https://doi.org/10.1021/ic0507159
    Published October 11, 2005
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