Synthesis, Magnetic Properties, and Incomplete Double-Cubane Structure of Manganese(III)-Metal(II) Complexes [Mn(MeOH)L(OH)M(bpy)]2 (M = Zn, Cu, Ni, and Mn; H4L = 1,2-Bis(2-hydroxybenzamido)benzene; bpy = 2,2′-Bipyridine)

Yukinari Sunatsuki, Hiromitsu Shimada, Toshihiro Matsuo, Masaaki Nakamura, Fumiaki Kai, Naohide Matsumoto, Nazzareno Re

Research output: Contribution to journalArticle

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Abstract

The manganese(III) complex K[MnL(py)2]·py (H4L = 1,2-bis(2-hydroxybenzamido)benzene, py = pyridine) reacted as a ligand complex at the two phenoxo oxygen atoms with metal(II) ion and 2,2′-bipyridine to give a series of heterometal complexes [Mn(MeOH)L(OH)M(bpy)h (M(II) = Zn (1); Cu (2); Ni (3); Mn (4)). X-ray structures were determined 1, C68H74N8O18Mn2Zn 2: n= 12.367(3) Å, α= 12.844(2) Å. c = 12.262(2) Å, α = 106.58(1)°, β= 117.89(1)°, γ = 78.57(2)°, triclinic, P1̄. and Z = 1. 2, C68H74N8O18Mn2Cu 2: a = 13.447(1) Å. b = 12.670-(2) Å. c = 21.732(1) Å, β = 107.076(5)°. monoclinic, P21/n, and Z=2. 3, C68H74N8O18Mn2Ni 2: a_= 12.358(3) Å, b = 12.847(3) Å, c= 12.315(3) Å, α= 106.63(2)°. β = 118.71(1)°, γ = 78.32(2)°, triclinic. P1̄, and Z = 1. 4. C66H66N8O16Mn4: a = 12.511(2) Å, b = 21.129(3) Å. c = 12.811(1) Å. β= 110.12(1)°, monoclinic. P21/n, and Z = 2. The X-ray analyses confirmed that each of the crystals consists of an incomplete double-cubane molecule with a [Mn2M2O6] core, in which two M(II) ions are bridged by two hydroxo groups to form a planar dinuclear moiety bridged by di-μ-hydroxo groups [(bpy)M(OH)2M(bpy)]2+ and the dinuclear moiety is sandwiched between two Mn(III) complexes [Mn(MeoH)L]-. The Mn(III) ion and the dinuclear M(II) moiety are triply bridged by the one hydroxo oxygen of the dinuclear moiety and two phenoxo oxygen atoms of the Mn(III) ligand complex. The two phenoxo oxygen atoms of the Mn(III) ligand complex coordinate as an axial ligand to two independent metal(II) ions of the dinuclear moiety. The magnetic susceptibilities of 1-4 were measured in the temperature range of 2-300 K. All the Mn(III) ions in these complexes are in a high-spin state of SMn = 2 with a d4 electronic configuration, and the metal(II) ions are in the spin states of SZn = 0, SCa = 1/2. SNi = 1, and SMn(11) = 1/2 (low-spin). The magnetic susceptibility data are well reproduced by the following spin Hamiltonian based on the rhombus spin coupling model with spin (S1, S2, S3, S4) = (2, SM, 2, SM), including a zero-field splitting term for the Mn(III) centers: H = gMnβ(S1 + S3)·H + gMβ(S2 + S4)·H - 2J(S1·S2 -f S2·S3 + S3-S4 + S4·S1) - 2J'(S2·S4) + DMn[S1z2 + S3z2], in which gMn and gM are the g factors of the Mn(III) and M(II) ions, J and J' are the Mn(III)-M(II) and M(II)-M(II) Heisenberg coupling constants, and D is the zero-field splitting parameter of Mn(III). The calculated best-fit parameters are as follows: gMn = 1.91, gCa = 2.39. J = -4.5 cm-1, J' = -8.1 cm-1, and DMn = -4.9 cm-1 for 2; gMn = 1.97, gNi = 2.23, J = -1.5 cm-1, J' = -2.6 cm-1, and DMn = -5.5 cm-1 for 3; and gMn =1.95, gMn(II) = 2.29. J = -3.5 cm-1, J' = -14.1 cm-1, and DMn = -12.0 cm-1 for 4. The spin frustration due to the incomplete double-cubane structure is discussed.

Original languageEnglish
Pages (from-to)5566-5574
Number of pages9
JournalInorganic Chemistry
Volume37
Issue number21
Publication statusPublished - 1998
Externally publishedYes

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Coordination Complexes
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manganese
Magnetic properties
Metals
benzene
magnetic properties
Metal ions
synthesis
metal ions
metals
Oxygen
Ligands
oxygen atoms
ligands
Magnetic susceptibility
Atoms
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  • Inorganic Chemistry

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Synthesis, Magnetic Properties, and Incomplete Double-Cubane Structure of Manganese(III)-Metal(II) Complexes [Mn(MeOH)L(OH)M(bpy)]2 (M = Zn, Cu, Ni, and Mn; H4L = 1,2-Bis(2-hydroxybenzamido)benzene; bpy = 2,2′-Bipyridine). / Sunatsuki, Yukinari; Shimada, Hiromitsu; Matsuo, Toshihiro; Nakamura, Masaaki; Kai, Fumiaki; Matsumoto, Naohide; Re, Nazzareno.

In: Inorganic Chemistry, Vol. 37, No. 21, 1998, p. 5566-5574.

Research output: Contribution to journalArticle

@article{6ba5f446caf9485892c328f515104e1c,
title = "Synthesis, Magnetic Properties, and Incomplete Double-Cubane Structure of Manganese(III)-Metal(II) Complexes [Mn(MeOH)L(OH)M(bpy)]2 (M = Zn, Cu, Ni, and Mn; H4L = 1,2-Bis(2-hydroxybenzamido)benzene; bpy = 2,2′-Bipyridine)",
abstract = "The manganese(III) complex K[MnL(py)2]·py (H4L = 1,2-bis(2-hydroxybenzamido)benzene, py = pyridine) reacted as a ligand complex at the two phenoxo oxygen atoms with metal(II) ion and 2,2′-bipyridine to give a series of heterometal complexes [Mn(MeOH)L(OH)M(bpy)h (M(II) = Zn (1); Cu (2); Ni (3); Mn (4)). X-ray structures were determined 1, C68H74N8O18Mn2Zn 2: n= 12.367(3) {\AA}, α= 12.844(2) {\AA}. c = 12.262(2) {\AA}, α = 106.58(1)°, β= 117.89(1)°, γ = 78.57(2)°, triclinic, P1̄. and Z = 1. 2, C68H74N8O18Mn2Cu 2: a = 13.447(1) {\AA}. b = 12.670-(2) {\AA}. c = 21.732(1) {\AA}, β = 107.076(5)°. monoclinic, P21/n, and Z=2. 3, C68H74N8O18Mn2Ni 2: a_= 12.358(3) {\AA}, b = 12.847(3) {\AA}, c= 12.315(3) {\AA}, α= 106.63(2)°. β = 118.71(1)°, γ = 78.32(2)°, triclinic. P1̄, and Z = 1. 4. C66H66N8O16Mn4: a = 12.511(2) {\AA}, b = 21.129(3) {\AA}. c = 12.811(1) {\AA}. β= 110.12(1)°, monoclinic. P21/n, and Z = 2. The X-ray analyses confirmed that each of the crystals consists of an incomplete double-cubane molecule with a [Mn2M2O6] core, in which two M(II) ions are bridged by two hydroxo groups to form a planar dinuclear moiety bridged by di-μ-hydroxo groups [(bpy)M(OH)2M(bpy)]2+ and the dinuclear moiety is sandwiched between two Mn(III) complexes [Mn(MeoH)L]-. The Mn(III) ion and the dinuclear M(II) moiety are triply bridged by the one hydroxo oxygen of the dinuclear moiety and two phenoxo oxygen atoms of the Mn(III) ligand complex. The two phenoxo oxygen atoms of the Mn(III) ligand complex coordinate as an axial ligand to two independent metal(II) ions of the dinuclear moiety. The magnetic susceptibilities of 1-4 were measured in the temperature range of 2-300 K. All the Mn(III) ions in these complexes are in a high-spin state of SMn = 2 with a d4 electronic configuration, and the metal(II) ions are in the spin states of SZn = 0, SCa = 1/2. SNi = 1, and SMn(11) = 1/2 (low-spin). The magnetic susceptibility data are well reproduced by the following spin Hamiltonian based on the rhombus spin coupling model with spin (S1, S2, S3, S4) = (2, SM, 2, SM), including a zero-field splitting term for the Mn(III) centers: H = gMnβ(S1 + S3)·H + gMβ(S2 + S4)·H - 2J(S1·S2 -f S2·S3 + S3-S4 + S4·S1) - 2J'(S2·S4) + DMn[S1z2 + S3z2], in which gMn and gM are the g factors of the Mn(III) and M(II) ions, J and J' are the Mn(III)-M(II) and M(II)-M(II) Heisenberg coupling constants, and D is the zero-field splitting parameter of Mn(III). The calculated best-fit parameters are as follows: gMn = 1.91, gCa = 2.39. J = -4.5 cm-1, J' = -8.1 cm-1, and DMn = -4.9 cm-1 for 2; gMn = 1.97, gNi = 2.23, J = -1.5 cm-1, J' = -2.6 cm-1, and DMn = -5.5 cm-1 for 3; and gMn =1.95, gMn(II) = 2.29. J = -3.5 cm-1, J' = -14.1 cm-1, and DMn = -12.0 cm-1 for 4. The spin frustration due to the incomplete double-cubane structure is discussed.",
author = "Yukinari Sunatsuki and Hiromitsu Shimada and Toshihiro Matsuo and Masaaki Nakamura and Fumiaki Kai and Naohide Matsumoto and Nazzareno Re",
year = "1998",
language = "English",
volume = "37",
pages = "5566--5574",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Synthesis, Magnetic Properties, and Incomplete Double-Cubane Structure of Manganese(III)-Metal(II) Complexes [Mn(MeOH)L(OH)M(bpy)]2 (M = Zn, Cu, Ni, and Mn; H4L = 1,2-Bis(2-hydroxybenzamido)benzene; bpy = 2,2′-Bipyridine)

AU - Sunatsuki, Yukinari

AU - Shimada, Hiromitsu

AU - Matsuo, Toshihiro

AU - Nakamura, Masaaki

AU - Kai, Fumiaki

AU - Matsumoto, Naohide

AU - Re, Nazzareno

PY - 1998

Y1 - 1998

N2 - The manganese(III) complex K[MnL(py)2]·py (H4L = 1,2-bis(2-hydroxybenzamido)benzene, py = pyridine) reacted as a ligand complex at the two phenoxo oxygen atoms with metal(II) ion and 2,2′-bipyridine to give a series of heterometal complexes [Mn(MeOH)L(OH)M(bpy)h (M(II) = Zn (1); Cu (2); Ni (3); Mn (4)). X-ray structures were determined 1, C68H74N8O18Mn2Zn 2: n= 12.367(3) Å, α= 12.844(2) Å. c = 12.262(2) Å, α = 106.58(1)°, β= 117.89(1)°, γ = 78.57(2)°, triclinic, P1̄. and Z = 1. 2, C68H74N8O18Mn2Cu 2: a = 13.447(1) Å. b = 12.670-(2) Å. c = 21.732(1) Å, β = 107.076(5)°. monoclinic, P21/n, and Z=2. 3, C68H74N8O18Mn2Ni 2: a_= 12.358(3) Å, b = 12.847(3) Å, c= 12.315(3) Å, α= 106.63(2)°. β = 118.71(1)°, γ = 78.32(2)°, triclinic. P1̄, and Z = 1. 4. C66H66N8O16Mn4: a = 12.511(2) Å, b = 21.129(3) Å. c = 12.811(1) Å. β= 110.12(1)°, monoclinic. P21/n, and Z = 2. The X-ray analyses confirmed that each of the crystals consists of an incomplete double-cubane molecule with a [Mn2M2O6] core, in which two M(II) ions are bridged by two hydroxo groups to form a planar dinuclear moiety bridged by di-μ-hydroxo groups [(bpy)M(OH)2M(bpy)]2+ and the dinuclear moiety is sandwiched between two Mn(III) complexes [Mn(MeoH)L]-. The Mn(III) ion and the dinuclear M(II) moiety are triply bridged by the one hydroxo oxygen of the dinuclear moiety and two phenoxo oxygen atoms of the Mn(III) ligand complex. The two phenoxo oxygen atoms of the Mn(III) ligand complex coordinate as an axial ligand to two independent metal(II) ions of the dinuclear moiety. The magnetic susceptibilities of 1-4 were measured in the temperature range of 2-300 K. All the Mn(III) ions in these complexes are in a high-spin state of SMn = 2 with a d4 electronic configuration, and the metal(II) ions are in the spin states of SZn = 0, SCa = 1/2. SNi = 1, and SMn(11) = 1/2 (low-spin). The magnetic susceptibility data are well reproduced by the following spin Hamiltonian based on the rhombus spin coupling model with spin (S1, S2, S3, S4) = (2, SM, 2, SM), including a zero-field splitting term for the Mn(III) centers: H = gMnβ(S1 + S3)·H + gMβ(S2 + S4)·H - 2J(S1·S2 -f S2·S3 + S3-S4 + S4·S1) - 2J'(S2·S4) + DMn[S1z2 + S3z2], in which gMn and gM are the g factors of the Mn(III) and M(II) ions, J and J' are the Mn(III)-M(II) and M(II)-M(II) Heisenberg coupling constants, and D is the zero-field splitting parameter of Mn(III). The calculated best-fit parameters are as follows: gMn = 1.91, gCa = 2.39. J = -4.5 cm-1, J' = -8.1 cm-1, and DMn = -4.9 cm-1 for 2; gMn = 1.97, gNi = 2.23, J = -1.5 cm-1, J' = -2.6 cm-1, and DMn = -5.5 cm-1 for 3; and gMn =1.95, gMn(II) = 2.29. J = -3.5 cm-1, J' = -14.1 cm-1, and DMn = -12.0 cm-1 for 4. The spin frustration due to the incomplete double-cubane structure is discussed.

AB - The manganese(III) complex K[MnL(py)2]·py (H4L = 1,2-bis(2-hydroxybenzamido)benzene, py = pyridine) reacted as a ligand complex at the two phenoxo oxygen atoms with metal(II) ion and 2,2′-bipyridine to give a series of heterometal complexes [Mn(MeOH)L(OH)M(bpy)h (M(II) = Zn (1); Cu (2); Ni (3); Mn (4)). X-ray structures were determined 1, C68H74N8O18Mn2Zn 2: n= 12.367(3) Å, α= 12.844(2) Å. c = 12.262(2) Å, α = 106.58(1)°, β= 117.89(1)°, γ = 78.57(2)°, triclinic, P1̄. and Z = 1. 2, C68H74N8O18Mn2Cu 2: a = 13.447(1) Å. b = 12.670-(2) Å. c = 21.732(1) Å, β = 107.076(5)°. monoclinic, P21/n, and Z=2. 3, C68H74N8O18Mn2Ni 2: a_= 12.358(3) Å, b = 12.847(3) Å, c= 12.315(3) Å, α= 106.63(2)°. β = 118.71(1)°, γ = 78.32(2)°, triclinic. P1̄, and Z = 1. 4. C66H66N8O16Mn4: a = 12.511(2) Å, b = 21.129(3) Å. c = 12.811(1) Å. β= 110.12(1)°, monoclinic. P21/n, and Z = 2. The X-ray analyses confirmed that each of the crystals consists of an incomplete double-cubane molecule with a [Mn2M2O6] core, in which two M(II) ions are bridged by two hydroxo groups to form a planar dinuclear moiety bridged by di-μ-hydroxo groups [(bpy)M(OH)2M(bpy)]2+ and the dinuclear moiety is sandwiched between two Mn(III) complexes [Mn(MeoH)L]-. The Mn(III) ion and the dinuclear M(II) moiety are triply bridged by the one hydroxo oxygen of the dinuclear moiety and two phenoxo oxygen atoms of the Mn(III) ligand complex. The two phenoxo oxygen atoms of the Mn(III) ligand complex coordinate as an axial ligand to two independent metal(II) ions of the dinuclear moiety. The magnetic susceptibilities of 1-4 were measured in the temperature range of 2-300 K. All the Mn(III) ions in these complexes are in a high-spin state of SMn = 2 with a d4 electronic configuration, and the metal(II) ions are in the spin states of SZn = 0, SCa = 1/2. SNi = 1, and SMn(11) = 1/2 (low-spin). The magnetic susceptibility data are well reproduced by the following spin Hamiltonian based on the rhombus spin coupling model with spin (S1, S2, S3, S4) = (2, SM, 2, SM), including a zero-field splitting term for the Mn(III) centers: H = gMnβ(S1 + S3)·H + gMβ(S2 + S4)·H - 2J(S1·S2 -f S2·S3 + S3-S4 + S4·S1) - 2J'(S2·S4) + DMn[S1z2 + S3z2], in which gMn and gM are the g factors of the Mn(III) and M(II) ions, J and J' are the Mn(III)-M(II) and M(II)-M(II) Heisenberg coupling constants, and D is the zero-field splitting parameter of Mn(III). The calculated best-fit parameters are as follows: gMn = 1.91, gCa = 2.39. J = -4.5 cm-1, J' = -8.1 cm-1, and DMn = -4.9 cm-1 for 2; gMn = 1.97, gNi = 2.23, J = -1.5 cm-1, J' = -2.6 cm-1, and DMn = -5.5 cm-1 for 3; and gMn =1.95, gMn(II) = 2.29. J = -3.5 cm-1, J' = -14.1 cm-1, and DMn = -12.0 cm-1 for 4. The spin frustration due to the incomplete double-cubane structure is discussed.

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M3 - Article

VL - 37

SP - 5566

EP - 5574

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 21

ER -