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American Chemical Society, Inorganic Chemistry, 2(42), p. 641-649, 2002

DOI: 10.1021/ic025669g

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Synthesis and Characterization of Heterodinuclear Ln3+−Fe3+and Ln3+−Co3+Complexes, Bridged by Cyanide Ligand (Ln3+= Lanthanide Ions). Nature of the Magnetic Interaction in the Ln3+−Fe3+Complexes

Journal article published in 2003 by Albert Figuerola, Carmen Diaz, Joan Ribas, Vassilis Tangoulis, Jaume Granell ORCID, Francesc Lloret, José Mahía, Miguel Maestro
This paper was not found in any repository; the policy of its publisher is unknown or unclear.
This paper was not found in any repository; the policy of its publisher is unknown or unclear.

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Abstract

The reaction of Ln(NO3)3.aq with K3[Fe(CN)6] or K3[Co(CN)6] in N,N'-dimethylformamide (DMF) led to 25 heterodinuclear [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O and [Ln(DMF)4(H2O)3(mu-CN)Co(CN)5].nH2O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr(3+)-Fe3+), (Tm(3+)-Fe3+), (Ce(3+)-Co3+), (Sm(3+)-Co3+), and (Yb(3+)-Co3+) have been structurally characterized; they crystallize in the equivalent monoclinic space groups P21/c or P21/n. Structural studies of these two families show that they are isomorphous. This relationship in conjunction with the diamagnetism of the Co3+ allows an approximation to the nature of coupling between the iron(III) and the lanthanide(III) ions in the [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O complexes. The Ln(3+)-Fe3+ interaction is antiferromagnetic for Ln = Ce, Nd, Gd, and Dy and ferromagnetic for Ln = Tb, Ho, and Tm. For Ln = Pr, Eu, Er, Sm, and Yb, there is no sign of any significant interaction. The isotropic nature of Gd3+ helps to evaluate the value of the exchange interaction.