Crystal structures and magnetic properties of complexes of M IICl2 (M = Cu, Ni, and Co) coordinated with 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine: 2D magnetic anisotropy of the aminoxyl-coIIcomplex in the crystalline state

Zhicheng Zhu, Satoru Karasawa, Noboru Koga

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Abstract

Three metal complexes, [MIICl2(NOPy-OMe)2] (M = Cu (1), Ni (2), and Co (3)), were prepared by mixing the corresponding metal chloride and 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine, 4NOPy-OMe, in 1:2 ratio. Complex 1 has two structures (complexes A and B) with similar coordination geometries, compressed octahedrons. In the crystal structure, complexes A and B locate alternately in short distances (C radical⋯ Cβ = 3.17 and 3.23 Å) to form a 1-D chain structure. Complexes 2 and 3 are isomorphous and have a slightly distorted octahedral structure. In the crystal structure, both complexes have intermolecular short contacts (Cradical⋯Cα = 3.46 and 3.52 Å for 2 and 3, respectively) to form the 2-D structures. The temperature dependence of the χmolT values for the three complexes indicated that the magnetic interactions between the radicals and the metal ions within the complexes were ferromagnetic. By fitting a modified Fisher 1-D model to the data of the χmolT vs T plot for 1, we estimated the intra- and intermolecular (intrachain) exchange coupling constants to be J1/KB = 60.2 and J2/kB = -7.02 K, respectively. On the other hand, complexes 2 and 3 showed steep increases of the χmolT value below ca. 3 K, indicating that the long-range magnetic ordering is operating. The 1/χmol vs T plot for 2 was analyzed by a Curie-Weiss model to give θ = 6.25 K and C = 2.02 cm 3 K mol-1 with gNi = 2.25. Complex 3 was investigated in more detail using an orientated sample. Magnetic behavior strongly depends on the direction of the applied field, in which the c* axis perpendicular to the ab plane is an easy axis for magnetization. Direct current (dc) and alternating current (ac) magnetic susceptibility measurements revealed that complex 3 had a magnetic phase transition of Tc = 2.14 K and exhibited a glasslike magnetic behavior below Tc.

Original languageEnglish
Pages (from-to)6004-6011
Number of pages8
JournalInorganic Chemistry
Volume44
Issue number17
DOIs
Publication statusPublished - Aug 22 2005

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Magnetic anisotropy
Magnetization
pyridines
Magnetic properties
Crystal structure
plots
octahedrons
magnetic properties
Crystalline materials
Exchange coupling
anisotropy
crystal structure
Coordination Complexes
Magnetic susceptibility
metals
Metal ions
Chlorides
metal ions
alternating current
Phase transitions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{32486c5108914b458c8faefe6b3cdfe4,
title = "Crystal structures and magnetic properties of complexes of M IICl2 (M = Cu, Ni, and Co) coordinated with 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine: 2D magnetic anisotropy of the aminoxyl-coIIcomplex in the crystalline state",
abstract = "Three metal complexes, [MIICl2(NOPy-OMe)2] (M = Cu (1), Ni (2), and Co (3)), were prepared by mixing the corresponding metal chloride and 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine, 4NOPy-OMe, in 1:2 ratio. Complex 1 has two structures (complexes A and B) with similar coordination geometries, compressed octahedrons. In the crystal structure, complexes A and B locate alternately in short distances (C radical⋯ Cβ = 3.17 and 3.23 {\AA}) to form a 1-D chain structure. Complexes 2 and 3 are isomorphous and have a slightly distorted octahedral structure. In the crystal structure, both complexes have intermolecular short contacts (Cradical⋯Cα = 3.46 and 3.52 {\AA} for 2 and 3, respectively) to form the 2-D structures. The temperature dependence of the χmolT values for the three complexes indicated that the magnetic interactions between the radicals and the metal ions within the complexes were ferromagnetic. By fitting a modified Fisher 1-D model to the data of the χmolT vs T plot for 1, we estimated the intra- and intermolecular (intrachain) exchange coupling constants to be J1/KB = 60.2 and J2/kB = -7.02 K, respectively. On the other hand, complexes 2 and 3 showed steep increases of the χmolT value below ca. 3 K, indicating that the long-range magnetic ordering is operating. The 1/χmol vs T plot for 2 was analyzed by a Curie-Weiss model to give θ = 6.25 K and C = 2.02 cm 3 K mol-1 with gNi = 2.25. Complex 3 was investigated in more detail using an orientated sample. Magnetic behavior strongly depends on the direction of the applied field, in which the c* axis perpendicular to the ab plane is an easy axis for magnetization. Direct current (dc) and alternating current (ac) magnetic susceptibility measurements revealed that complex 3 had a magnetic phase transition of Tc = 2.14 K and exhibited a glasslike magnetic behavior below Tc.",
author = "Zhicheng Zhu and Satoru Karasawa and Noboru Koga",
year = "2005",
month = "8",
day = "22",
doi = "10.1021/ic048441x",
language = "English",
volume = "44",
pages = "6004--6011",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "17",

}

TY - JOUR

T1 - Crystal structures and magnetic properties of complexes of M IICl2 (M = Cu, Ni, and Co) coordinated with 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine

T2 - 2D magnetic anisotropy of the aminoxyl-coIIcomplex in the crystalline state

AU - Zhu, Zhicheng

AU - Karasawa, Satoru

AU - Koga, Noboru

PY - 2005/8/22

Y1 - 2005/8/22

N2 - Three metal complexes, [MIICl2(NOPy-OMe)2] (M = Cu (1), Ni (2), and Co (3)), were prepared by mixing the corresponding metal chloride and 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine, 4NOPy-OMe, in 1:2 ratio. Complex 1 has two structures (complexes A and B) with similar coordination geometries, compressed octahedrons. In the crystal structure, complexes A and B locate alternately in short distances (C radical⋯ Cβ = 3.17 and 3.23 Å) to form a 1-D chain structure. Complexes 2 and 3 are isomorphous and have a slightly distorted octahedral structure. In the crystal structure, both complexes have intermolecular short contacts (Cradical⋯Cα = 3.46 and 3.52 Å for 2 and 3, respectively) to form the 2-D structures. The temperature dependence of the χmolT values for the three complexes indicated that the magnetic interactions between the radicals and the metal ions within the complexes were ferromagnetic. By fitting a modified Fisher 1-D model to the data of the χmolT vs T plot for 1, we estimated the intra- and intermolecular (intrachain) exchange coupling constants to be J1/KB = 60.2 and J2/kB = -7.02 K, respectively. On the other hand, complexes 2 and 3 showed steep increases of the χmolT value below ca. 3 K, indicating that the long-range magnetic ordering is operating. The 1/χmol vs T plot for 2 was analyzed by a Curie-Weiss model to give θ = 6.25 K and C = 2.02 cm 3 K mol-1 with gNi = 2.25. Complex 3 was investigated in more detail using an orientated sample. Magnetic behavior strongly depends on the direction of the applied field, in which the c* axis perpendicular to the ab plane is an easy axis for magnetization. Direct current (dc) and alternating current (ac) magnetic susceptibility measurements revealed that complex 3 had a magnetic phase transition of Tc = 2.14 K and exhibited a glasslike magnetic behavior below Tc.

AB - Three metal complexes, [MIICl2(NOPy-OMe)2] (M = Cu (1), Ni (2), and Co (3)), were prepared by mixing the corresponding metal chloride and 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine, 4NOPy-OMe, in 1:2 ratio. Complex 1 has two structures (complexes A and B) with similar coordination geometries, compressed octahedrons. In the crystal structure, complexes A and B locate alternately in short distances (C radical⋯ Cβ = 3.17 and 3.23 Å) to form a 1-D chain structure. Complexes 2 and 3 are isomorphous and have a slightly distorted octahedral structure. In the crystal structure, both complexes have intermolecular short contacts (Cradical⋯Cα = 3.46 and 3.52 Å for 2 and 3, respectively) to form the 2-D structures. The temperature dependence of the χmolT values for the three complexes indicated that the magnetic interactions between the radicals and the metal ions within the complexes were ferromagnetic. By fitting a modified Fisher 1-D model to the data of the χmolT vs T plot for 1, we estimated the intra- and intermolecular (intrachain) exchange coupling constants to be J1/KB = 60.2 and J2/kB = -7.02 K, respectively. On the other hand, complexes 2 and 3 showed steep increases of the χmolT value below ca. 3 K, indicating that the long-range magnetic ordering is operating. The 1/χmol vs T plot for 2 was analyzed by a Curie-Weiss model to give θ = 6.25 K and C = 2.02 cm 3 K mol-1 with gNi = 2.25. Complex 3 was investigated in more detail using an orientated sample. Magnetic behavior strongly depends on the direction of the applied field, in which the c* axis perpendicular to the ab plane is an easy axis for magnetization. Direct current (dc) and alternating current (ac) magnetic susceptibility measurements revealed that complex 3 had a magnetic phase transition of Tc = 2.14 K and exhibited a glasslike magnetic behavior below Tc.

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U2 - 10.1021/ic048441x

DO - 10.1021/ic048441x

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