Synthesis, structures, and magnetic properties of face-sharing heterodinuclear Ni(II)-Ln(III) (Ln = Eu, Gd, Tb, Dy) complexes

Tomoka Yamaguchi, Yukinari Sunatsuki, Hiroyuki Ishida, Masaaki Kojima, Hamo Akashi, Nazzareno Re, Naohide Matsumoto, Andrzej Pochaba, Jerzy Mroziński

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Abstract

Heterodinuclear [(NiIIL)LnIII(hfac) 2(EtOH)] (H3L = 1,1,1-tris[(salicylideneamino)methyl] ethane; Ln = Eu, Gd, Tb, and Dy; hfac = hexafluoroacetylacetonate) complexes (1·Ln) were prepared by treating [Ni(H1.5L)]Cl0.5 (1) with [Ln(hfac)3(H2O)2] and triethylamine in ethanol (1:1:1). All 1·Ln complexes (1·Eu, 1·Gd, 1·Tb, and 1·Dy) crystallized in the triclinic space group P1 (No. 2) with Z = 2 with very similar structures. Each complex is a face-sharing dinuclear molecule. The NiII ion is coordinated by the L3- ligand in a N3O3 coordination sphere, and the three phenolate oxygen atoms coordinate to an LnIII ion as bridging atoms. The LnIII ion is eight-coordinate, with four oxygen atoms of two hfac-,s, three phenolate oxygen atoms of L3-, and one ethanol oxygen atom coordinated. Temperature-dependent magnetic susceptibility and field-dependent magnetization measurements showed a ferromagnetic interaction between NiII and GdIII in 1·Gd. The NiII-LnIII magnetic interactions in 1·Eu, 1·Tb, and 1·Dy were evaluated by comparing their magnetic susceptibilities with those of the isostructural ZnII-Ln III complexes, [(ZnL)Ln(hfac)2(EtOH)] (2·Ln) containing a diamagnetic ZnII ion. A ferromagnetic interaction was indicated in 1·Tb and 1·Dy, while the interaction between Ni II and EuIII was negligible in 1·Eu. The magnetic behaviors of 1·Dy and 2·Dy were analyzed theoretically to give insight into the sublevel structures of the DyIII ion and its coupling with NiII. Frequency dependence in the ac susceptibility signals was observed in 1·Dy.

Original languageEnglish
Pages (from-to)5736-5745
Number of pages10
JournalInorganic Chemistry
Volume47
Issue number13
DOIs
Publication statusPublished - Jul 7 2008

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Magnetic properties
Ions
magnetic properties
oxygen atoms
Atoms
Oxygen
synthesis
ions
Magnetic susceptibility
magnetic permeability
ethyl alcohol
Ethanol
interactions
Ethane
ethane
Magnetization
Magnetic fields
Ligands
magnetization
ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

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Synthesis, structures, and magnetic properties of face-sharing heterodinuclear Ni(II)-Ln(III) (Ln = Eu, Gd, Tb, Dy) complexes. / Yamaguchi, Tomoka; Sunatsuki, Yukinari; Ishida, Hiroyuki; Kojima, Masaaki; Akashi, Hamo; Re, Nazzareno; Matsumoto, Naohide; Pochaba, Andrzej; Mroziński, Jerzy.

In: Inorganic Chemistry, Vol. 47, No. 13, 07.07.2008, p. 5736-5745.

Research output: Contribution to journalArticle

Yamaguchi, Tomoka ; Sunatsuki, Yukinari ; Ishida, Hiroyuki ; Kojima, Masaaki ; Akashi, Hamo ; Re, Nazzareno ; Matsumoto, Naohide ; Pochaba, Andrzej ; Mroziński, Jerzy. / Synthesis, structures, and magnetic properties of face-sharing heterodinuclear Ni(II)-Ln(III) (Ln = Eu, Gd, Tb, Dy) complexes. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 13. pp. 5736-5745.
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abstract = "Heterodinuclear [(NiIIL)LnIII(hfac) 2(EtOH)] (H3L = 1,1,1-tris[(salicylideneamino)methyl] ethane; Ln = Eu, Gd, Tb, and Dy; hfac = hexafluoroacetylacetonate) complexes (1·Ln) were prepared by treating [Ni(H1.5L)]Cl0.5 (1) with [Ln(hfac)3(H2O)2] and triethylamine in ethanol (1:1:1). All 1·Ln complexes (1·Eu, 1·Gd, 1·Tb, and 1·Dy) crystallized in the triclinic space group P1 (No. 2) with Z = 2 with very similar structures. Each complex is a face-sharing dinuclear molecule. The NiII ion is coordinated by the L3- ligand in a N3O3 coordination sphere, and the three phenolate oxygen atoms coordinate to an LnIII ion as bridging atoms. The LnIII ion is eight-coordinate, with four oxygen atoms of two hfac-,s, three phenolate oxygen atoms of L3-, and one ethanol oxygen atom coordinated. Temperature-dependent magnetic susceptibility and field-dependent magnetization measurements showed a ferromagnetic interaction between NiII and GdIII in 1·Gd. The NiII-LnIII magnetic interactions in 1·Eu, 1·Tb, and 1·Dy were evaluated by comparing their magnetic susceptibilities with those of the isostructural ZnII-Ln III complexes, [(ZnL)Ln(hfac)2(EtOH)] (2·Ln) containing a diamagnetic ZnII ion. A ferromagnetic interaction was indicated in 1·Tb and 1·Dy, while the interaction between Ni II and EuIII was negligible in 1·Eu. The magnetic behaviors of 1·Dy and 2·Dy were analyzed theoretically to give insight into the sublevel structures of the DyIII ion and its coupling with NiII. Frequency dependence in the ac susceptibility signals was observed in 1·Dy.",
author = "Tomoka Yamaguchi and Yukinari Sunatsuki and Hiroyuki Ishida and Masaaki Kojima and Hamo Akashi and Nazzareno Re and Naohide Matsumoto and Andrzej Pochaba and Jerzy Mroziński",
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T1 - Synthesis, structures, and magnetic properties of face-sharing heterodinuclear Ni(II)-Ln(III) (Ln = Eu, Gd, Tb, Dy) complexes

AU - Yamaguchi, Tomoka

AU - Sunatsuki, Yukinari

AU - Ishida, Hiroyuki

AU - Kojima, Masaaki

AU - Akashi, Hamo

AU - Re, Nazzareno

AU - Matsumoto, Naohide

AU - Pochaba, Andrzej

AU - Mroziński, Jerzy

PY - 2008/7/7

Y1 - 2008/7/7

N2 - Heterodinuclear [(NiIIL)LnIII(hfac) 2(EtOH)] (H3L = 1,1,1-tris[(salicylideneamino)methyl] ethane; Ln = Eu, Gd, Tb, and Dy; hfac = hexafluoroacetylacetonate) complexes (1·Ln) were prepared by treating [Ni(H1.5L)]Cl0.5 (1) with [Ln(hfac)3(H2O)2] and triethylamine in ethanol (1:1:1). All 1·Ln complexes (1·Eu, 1·Gd, 1·Tb, and 1·Dy) crystallized in the triclinic space group P1 (No. 2) with Z = 2 with very similar structures. Each complex is a face-sharing dinuclear molecule. The NiII ion is coordinated by the L3- ligand in a N3O3 coordination sphere, and the three phenolate oxygen atoms coordinate to an LnIII ion as bridging atoms. The LnIII ion is eight-coordinate, with four oxygen atoms of two hfac-,s, three phenolate oxygen atoms of L3-, and one ethanol oxygen atom coordinated. Temperature-dependent magnetic susceptibility and field-dependent magnetization measurements showed a ferromagnetic interaction between NiII and GdIII in 1·Gd. The NiII-LnIII magnetic interactions in 1·Eu, 1·Tb, and 1·Dy were evaluated by comparing their magnetic susceptibilities with those of the isostructural ZnII-Ln III complexes, [(ZnL)Ln(hfac)2(EtOH)] (2·Ln) containing a diamagnetic ZnII ion. A ferromagnetic interaction was indicated in 1·Tb and 1·Dy, while the interaction between Ni II and EuIII was negligible in 1·Eu. The magnetic behaviors of 1·Dy and 2·Dy were analyzed theoretically to give insight into the sublevel structures of the DyIII ion and its coupling with NiII. Frequency dependence in the ac susceptibility signals was observed in 1·Dy.

AB - Heterodinuclear [(NiIIL)LnIII(hfac) 2(EtOH)] (H3L = 1,1,1-tris[(salicylideneamino)methyl] ethane; Ln = Eu, Gd, Tb, and Dy; hfac = hexafluoroacetylacetonate) complexes (1·Ln) were prepared by treating [Ni(H1.5L)]Cl0.5 (1) with [Ln(hfac)3(H2O)2] and triethylamine in ethanol (1:1:1). All 1·Ln complexes (1·Eu, 1·Gd, 1·Tb, and 1·Dy) crystallized in the triclinic space group P1 (No. 2) with Z = 2 with very similar structures. Each complex is a face-sharing dinuclear molecule. The NiII ion is coordinated by the L3- ligand in a N3O3 coordination sphere, and the three phenolate oxygen atoms coordinate to an LnIII ion as bridging atoms. The LnIII ion is eight-coordinate, with four oxygen atoms of two hfac-,s, three phenolate oxygen atoms of L3-, and one ethanol oxygen atom coordinated. Temperature-dependent magnetic susceptibility and field-dependent magnetization measurements showed a ferromagnetic interaction between NiII and GdIII in 1·Gd. The NiII-LnIII magnetic interactions in 1·Eu, 1·Tb, and 1·Dy were evaluated by comparing their magnetic susceptibilities with those of the isostructural ZnII-Ln III complexes, [(ZnL)Ln(hfac)2(EtOH)] (2·Ln) containing a diamagnetic ZnII ion. A ferromagnetic interaction was indicated in 1·Tb and 1·Dy, while the interaction between Ni II and EuIII was negligible in 1·Eu. The magnetic behaviors of 1·Dy and 2·Dy were analyzed theoretically to give insight into the sublevel structures of the DyIII ion and its coupling with NiII. Frequency dependence in the ac susceptibility signals was observed in 1·Dy.

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