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

Albert Figuerola; Carmen Diaz; Joan Ribas; Vassilis Tangoulis; Jaume Granell; Francesc Lloret; José Mahía; Miguel Maestro

doi:10.1021/ic025669g

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

Albert Figuerola, Carmen Diaz^*, Joan Ribas, Vassilis Tangoulis, Jaume Granell, Francesc Lloret, José Mahía, Miguel Maestro

^*Corresponding author for this work

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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(μ-CN)Fe(CN) ₅]·nH₂O and [Ln(DMF)₄(H₂O)₃(μ-CN)Co (CN)₅]·nH₂O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr³⁺-Fe³⁺), (Tm³⁺-Fe³⁺), (Ce³⁺- Co³⁺), (Sm³⁺-Co³⁺), and (Yb³⁺-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(μ-CN)Fe (CN)₅]·nH₂O complexes. The Ln³⁺-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.

Original language	English (US)
Pages (from-to)	641-649
Number of pages	9
Journal	Inorganic chemistry
Volume	42
Issue number	2
DOIs	https://doi.org/10.1021/ic025669g
State	Published - Jan 27 2003
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Figuerola, A., Diaz, C., Ribas, J., Tangoulis, V., Granell, J., Lloret, F., Mahía, J., & Maestro, M. (2003). 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. Inorganic chemistry, 42(2), 641-649. https://doi.org/10.1021/ic025669g

@article{436d3258b50b4de89ad12d705c66bd59,

title = "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",

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(μ-CN)Fe(CN) 5]·nH2O and [Ln(DMF)4(H2O)3(μ-CN)Co (CN)5]·nH2O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr3+-Fe3+), (Tm3+-Fe3+), (Ce3+- Co3+), (Sm3+-Co3+), and (Yb3+-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(μ-CN)Fe (CN)5]·nH2O complexes. The Ln3+-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.",

author = "Albert Figuerola and Carmen Diaz and Joan Ribas and Vassilis Tangoulis and Jaume Granell and Francesc Lloret and Jos{\'e} Mah{\'i}a and Miguel Maestro",

year = "2003",

month = jan,

day = "27",

doi = "10.1021/ic025669g",

language = "English (US)",

volume = "42",

pages = "641--649",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "2",

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Figuerola, A, Diaz, C, Ribas, J, Tangoulis, V, Granell, J, Lloret, F, Mahía, J & Maestro, M 2003, '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', Inorganic chemistry, vol. 42, no. 2, pp. 641-649. https://doi.org/10.1021/ic025669g

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. / Figuerola, Albert; Diaz, Carmen; Ribas, Joan et al.
In: Inorganic chemistry, Vol. 42, No. 2, 27.01.2003, p. 641-649.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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

AU - Figuerola, Albert

AU - Diaz, Carmen

AU - Ribas, Joan

AU - Tangoulis, Vassilis

AU - Granell, Jaume

AU - Lloret, Francesc

AU - Mahía, José

AU - Maestro, Miguel

PY - 2003/1/27

Y1 - 2003/1/27

N2 - 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(μ-CN)Fe(CN) 5]·nH2O and [Ln(DMF)4(H2O)3(μ-CN)Co (CN)5]·nH2O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr3+-Fe3+), (Tm3+-Fe3+), (Ce3+- Co3+), (Sm3+-Co3+), and (Yb3+-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(μ-CN)Fe (CN)5]·nH2O complexes. The Ln3+-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.

AB - 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(μ-CN)Fe(CN) 5]·nH2O and [Ln(DMF)4(H2O)3(μ-CN)Co (CN)5]·nH2O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr3+-Fe3+), (Tm3+-Fe3+), (Ce3+- Co3+), (Sm3+-Co3+), and (Yb3+-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(μ-CN)Fe (CN)5]·nH2O complexes. The Ln3+-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.

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U2 - 10.1021/ic025669g

DO - 10.1021/ic025669g

M3 - Article

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AN - SCOPUS:0037467767

SN - 0020-1669

VL - 42

SP - 641

EP - 649

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 2

ER -

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

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