Heterodinuclear Complexes Containing d- and f-block Elements: Synthesis, Structural Characterization, and Metal-Metal Interactions of Novel Chromium(III)-Lanthanide(III) Compounds Bridged by Oxalate

Takayuki Sanada, Takayoshi Suzuki, Takafumi Yoshida, Sumio Kaizaki

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The reaction of Ln(III) ions with a tripodal ligand HBpz3- (hydrotris(pyrazol-1-yl)borate) and a "complex ligand" [Cr(acac)2(ox)]- (acac- = acetylacetonate, ox2- = oxalate) in aqueous solution afforded a series of the novel 3d-4f heterodinuclear complexes [(acac)2Cr(ox)Ln(HBpz3)2] (Ln = Eu (1), Gd (2), Tb (3), Yb (4), Lu (5)). The crystal structure of 4 has been determined by X-ray diffraction. Complex 4 crystallizes in monoclinic space group P2/n, of which the cell parameters are a = 8.594(3) Å, b = 18.538(4) Å, c = 12.093(2) Å, β = 93.71(2)°, and Z = 2. The Yb atom has an eight-coordinate distorted square antiprismatic coordination geometry. The intramolecular Cr⋯Yb distance is 5.631(1) Å. The magnetic susceptibility data for complex 2 showed that the CrIII-GdIII interaction is weakly antiferromagnetic with an exchange coupling constant JCrGd = -0.09 cm-1. The luminescence measurements demonstrated the energy transfers for both Ln(III) → Cr(III) and Cr(III) → Ln(III), of which the degree of emission quenching depends on the energy gap of the excited levels in two metal centers. These results reveal that the metal-metal interactions between Cr(III) and Ln(III) are very weak in magnetic interaction but are strong from the viewpoint of energy transfer.

Original languageEnglish
Pages (from-to)4712-4717
Number of pages6
JournalInorganic Chemistry
Issue number18
Publication statusPublished - Sep 7 1998
Externally publishedYes


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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