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 language | English |
|---|---|
| Pages (from-to) | 5507-5512 |
| Number of pages | 6 |
| Journal | Inorganic Chemistry |
| Volume | 42 |
| Issue number | 18 |
| DOIs | |
| Publication status | Published - Sep 8 2003 |
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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 journal › Article
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TY - JOUR
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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U2 - 10.1021/ic0344012
DO - 10.1021/ic0344012
M3 - Article
VL - 42
SP - 5507
EP - 5512
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 18
ER -