Synthesis and magnetic properties of heterometal cyclic tetranuclear complexes [CuIILMII(hfac)]2 (MII = Zn, Cu, Ni, Co, Fe, Mn; H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane; Hhfac = hexafluoroacetylacetone)

Shutaro Osa, Yukinari Sunatsuki, Yoko Yamamoto, Masaaki Nakamura, Tomoshige Shimamoto, Naohide Matsumoto, Nazzareno Re

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Abstract

A series of heterometal cyclic tetranuclear complexes [Cu IILMII(hfac)]2 (MII = Zn (1), Cu (2), Ni (3), Co (4), Fe(5), and Mn (6)) have been synthesized by the assembly reaction of K[CuL] and [MII(hfac)2(H2O) 2] with a 1:1 mole ratio in methanol, where H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane and Hhfac = hexafluoroacetylacetone. The crystal structures of 2, 4, and [Cu IILMnII(acac)]2 (6a) (Hacac = acetylacetone) were determined by single-crystal X-ray analyses. Each complex has a cyclic tetranuclear CuII2MII2 structure, in which the CuII complex functions as a "bridging ligand complex", and the CuII and MII ions are alternately arrayed. One side of the planar CuII complex coordinates to one M" ion at the two phenoxo and the methoxy oxygen atoms, and the opposite side of the CuII complex coordinates to another M" ion at the amido oxygen atom. The temperature-dependent magnetic susceptibilities revealed spin states of SM = 0, 1/2, 1, 3/2, 2, and 5/2 for the Zn II, CuII, NiII, CoII, Fe II, and MnII ions, respectively. Satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a rectangular arrangement with two different g-factors for the CuII and MII ions, two different isotropic magnetic exchange interactions, J1 and J2, between the CuII and M II ions, and a zero-field splitting term for the MII ion. In all cases, the antiferromagnetic coupling constants were found for both exchange interactions suggesting nonzero spin ground states with ST = 2|SM - SCu|, which were confirmed by the analysis of the field-dependent magnetization measurements.

Original languageEnglish
Pages (from-to)5507-5512
Number of pages6
JournalInorganic Chemistry
Volume42
Issue number18
DOIs
Publication statusPublished - Sep 8 2003

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Ethane
ethane
Magnetic properties
Ions
magnetic properties
synthesis
ions
Exchange interactions
Magnetic susceptibility
oxygen atoms
Oxygen
magnetic permeability
acetylacetone
Atoms
Ground state
Methanol
Magnetization
methyl alcohol
assembly
Crystal structure

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  • Inorganic Chemistry

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Synthesis and magnetic properties of heterometal cyclic tetranuclear complexes [CuIILMII(hfac)]2 (MII = Zn, Cu, Ni, Co, Fe, Mn; H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane; Hhfac = hexafluoroacetylacetone). / Osa, Shutaro; Sunatsuki, Yukinari; Yamamoto, Yoko; Nakamura, Masaaki; Shimamoto, Tomoshige; Matsumoto, Naohide; Re, Nazzareno.

In: Inorganic Chemistry, Vol. 42, No. 18, 08.09.2003, p. 5507-5512.

Research output: Contribution to journalArticle

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title = "Synthesis and magnetic properties of heterometal cyclic tetranuclear complexes [CuIILMII(hfac)]2 (MII = Zn, Cu, Ni, Co, Fe, Mn; H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane; Hhfac = hexafluoroacetylacetone)",
abstract = "A series of heterometal cyclic tetranuclear complexes [Cu IILMII(hfac)]2 (MII = Zn (1), Cu (2), Ni (3), Co (4), Fe(5), and Mn (6)) have been synthesized by the assembly reaction of K[CuL] and [MII(hfac)2(H2O) 2] with a 1:1 mole ratio in methanol, where H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane and Hhfac = hexafluoroacetylacetone. The crystal structures of 2, 4, and [Cu IILMnII(acac)]2 (6a) (Hacac = acetylacetone) were determined by single-crystal X-ray analyses. Each complex has a cyclic tetranuclear CuII2MII2 structure, in which the CuII complex functions as a {"}bridging ligand complex{"}, and the CuII and MII ions are alternately arrayed. One side of the planar CuII complex coordinates to one M{"} ion at the two phenoxo and the methoxy oxygen atoms, and the opposite side of the CuII complex coordinates to another M{"} ion at the amido oxygen atom. The temperature-dependent magnetic susceptibilities revealed spin states of SM = 0, 1/2, 1, 3/2, 2, and 5/2 for the Zn II, CuII, NiII, CoII, Fe II, and MnII ions, respectively. Satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a rectangular arrangement with two different g-factors for the CuII and MII ions, two different isotropic magnetic exchange interactions, J1 and J2, between the CuII and M II ions, and a zero-field splitting term for the MII ion. In all cases, the antiferromagnetic coupling constants were found for both exchange interactions suggesting nonzero spin ground states with ST = 2|SM - SCu|, which were confirmed by the analysis of the field-dependent magnetization measurements.",
author = "Shutaro Osa and Yukinari Sunatsuki and Yoko Yamamoto and Masaaki Nakamura and Tomoshige Shimamoto and Naohide Matsumoto and Nazzareno Re",
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T1 - Synthesis and magnetic properties of heterometal cyclic tetranuclear complexes [CuIILMII(hfac)]2 (MII = Zn, Cu, Ni, Co, Fe, Mn; H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane; Hhfac = hexafluoroacetylacetone)

AU - Osa, Shutaro

AU - Sunatsuki, Yukinari

AU - Yamamoto, Yoko

AU - Nakamura, Masaaki

AU - Shimamoto, Tomoshige

AU - Matsumoto, Naohide

AU - Re, Nazzareno

PY - 2003/9/8

Y1 - 2003/9/8

N2 - A series of heterometal cyclic tetranuclear complexes [Cu IILMII(hfac)]2 (MII = Zn (1), Cu (2), Ni (3), Co (4), Fe(5), and Mn (6)) have been synthesized by the assembly reaction of K[CuL] and [MII(hfac)2(H2O) 2] with a 1:1 mole ratio in methanol, where H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane and Hhfac = hexafluoroacetylacetone. The crystal structures of 2, 4, and [Cu IILMnII(acac)]2 (6a) (Hacac = acetylacetone) were determined by single-crystal X-ray analyses. Each complex has a cyclic tetranuclear CuII2MII2 structure, in which the CuII complex functions as a "bridging ligand complex", and the CuII and MII ions are alternately arrayed. One side of the planar CuII complex coordinates to one M" ion at the two phenoxo and the methoxy oxygen atoms, and the opposite side of the CuII complex coordinates to another M" ion at the amido oxygen atom. The temperature-dependent magnetic susceptibilities revealed spin states of SM = 0, 1/2, 1, 3/2, 2, and 5/2 for the Zn II, CuII, NiII, CoII, Fe II, and MnII ions, respectively. Satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a rectangular arrangement with two different g-factors for the CuII and MII ions, two different isotropic magnetic exchange interactions, J1 and J2, between the CuII and M II ions, and a zero-field splitting term for the MII ion. In all cases, the antiferromagnetic coupling constants were found for both exchange interactions suggesting nonzero spin ground states with ST = 2|SM - SCu|, which were confirmed by the analysis of the field-dependent magnetization measurements.

AB - A series of heterometal cyclic tetranuclear complexes [Cu IILMII(hfac)]2 (MII = Zn (1), Cu (2), Ni (3), Co (4), Fe(5), and Mn (6)) have been synthesized by the assembly reaction of K[CuL] and [MII(hfac)2(H2O) 2] with a 1:1 mole ratio in methanol, where H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane and Hhfac = hexafluoroacetylacetone. The crystal structures of 2, 4, and [Cu IILMnII(acac)]2 (6a) (Hacac = acetylacetone) were determined by single-crystal X-ray analyses. Each complex has a cyclic tetranuclear CuII2MII2 structure, in which the CuII complex functions as a "bridging ligand complex", and the CuII and MII ions are alternately arrayed. One side of the planar CuII complex coordinates to one M" ion at the two phenoxo and the methoxy oxygen atoms, and the opposite side of the CuII complex coordinates to another M" ion at the amido oxygen atom. The temperature-dependent magnetic susceptibilities revealed spin states of SM = 0, 1/2, 1, 3/2, 2, and 5/2 for the Zn II, CuII, NiII, CoII, Fe II, and MnII ions, respectively. Satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a rectangular arrangement with two different g-factors for the CuII and MII ions, two different isotropic magnetic exchange interactions, J1 and J2, between the CuII and M II ions, and a zero-field splitting term for the MII ion. In all cases, the antiferromagnetic coupling constants were found for both exchange interactions suggesting nonzero spin ground states with ST = 2|SM - SCu|, which were confirmed by the analysis of the field-dependent magnetization measurements.

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