High-frequency, high-field EPR; magnetic susceptibility; and X-ray studies on a ferromagnetic heterometallic complex of diethanolamine (H2L), [Cu4(NH3)4(HL)4][CdBr4]Br2·3dmf·H2O

E.A. Buvaylo, V.N. Kokozay, O.Y. Vassilyeva, Brian Skelton, J. Jezierska, L.C. Brunel, A. Ozarowski

Research output: Contribution to journalArticle

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Abstract

The novel heterometallic complex [Cu-4(NH3)(4)(HL)(4)][CdBr4]Br-2.3dmf.H2O has been prepared in the reaction of zerovalent copper with cadmium oxide in the air-exposed solution of ammonium bromide and diethanolamine (H2L) in dimethylformamide (dmf). The compound is monoclinic, with space group P2(1)/c, a = 14.876(3) Angstrom, b = 33.018-(6) Angstrom, c = 11.437(2) Angstrom, beta = 108.182(3)degrees, and Z = 4. The crystal lattice consists of [CU4(NH3)(4)(HL)(4)](4+) cations, [CdBr4](2-), Br- anions, and uncoordinated dmf and water molecules. In the cation, four independent Cu atoms occupy vertexes of a distorted tetrahedron with bridged (CuCu)-Cu-... distances in the range 3.127(2)-3.333(3) Angstrom and other (CuCu)-Cu-... separations being 3.445(3)-3.503(2) Angstrom. The magnetic susceptibility and the EPR spectra were measured over the temperature ranges 1.8-300 and 3-300 K, respectively. The magnetic moment was found to increase with decreasing temperature to reach a maximum of 2.60 mu(B) per one copper atom at ca. 10 K and was found, subsequently, to diminish slightly at lower temperatures owing to zero-field and Zeeman splitting of the S = 2 ground state. The temperature dependence of the magnetic susceptibility was fitted to the spin Hamiltonian H = J(ab)S(a)S(b) + J(bc)S(b)S(c), + J(cd)S(c)S(d), + J(ad)S(a)S(d) J(ac)S(a)S(c) + J(bd)S(b)S(d) with the exchange integrals J(ab) = J(bc), = J(cd) = J(ad) = -65(3) cm(-1) and J(ac) = J(bd) = + 1(3) cm(-1). High-field, high-frequency (95-380 GHz) EPR spectra due to an S = 2 ground state were simulated with g(x) = 2.138(1), g(y) = 2.142(1), g(z) = 2.067(1), D = -0.3529(3) cm(-1), and E = -0.0469(8) cm(-1). Calculations based on the X-ray structure indicate a negligible contribution of the magnetic dipole-dipole interactions to the zfs parameters D and E. A discussion of the isotropic and anisotropic exchange interactions and their effect on the zfs parameters is also given.
Original languageEnglish
Pages (from-to)206-216
JournalInorganic Chemistry
Volume44
Issue number2
DOIs
Publication statusPublished - 2005

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diethanolamine
Magnetic susceptibility
Paramagnetic resonance
magnetic permeability
cations
X rays
copper
Dimethylformamide
ammonium bromides
ground state
magnetic dipoles
crystal lattices
tetrahedrons
cadmium
Ground state
atoms
Cations
Copper
apexes
x rays

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@article{f0fd70d7af9d47a594ad8c1dd5836108,
title = "High-frequency, high-field EPR; magnetic susceptibility; and X-ray studies on a ferromagnetic heterometallic complex of diethanolamine (H2L), [Cu4(NH3)4(HL)4][CdBr4]Br2·3dmf·H2O",
abstract = "The novel heterometallic complex [Cu-4(NH3)(4)(HL)(4)][CdBr4]Br-2.3dmf.H2O has been prepared in the reaction of zerovalent copper with cadmium oxide in the air-exposed solution of ammonium bromide and diethanolamine (H2L) in dimethylformamide (dmf). The compound is monoclinic, with space group P2(1)/c, a = 14.876(3) Angstrom, b = 33.018-(6) Angstrom, c = 11.437(2) Angstrom, beta = 108.182(3)degrees, and Z = 4. The crystal lattice consists of [CU4(NH3)(4)(HL)(4)](4+) cations, [CdBr4](2-), Br- anions, and uncoordinated dmf and water molecules. In the cation, four independent Cu atoms occupy vertexes of a distorted tetrahedron with bridged (CuCu)-Cu-... distances in the range 3.127(2)-3.333(3) Angstrom and other (CuCu)-Cu-... separations being 3.445(3)-3.503(2) Angstrom. The magnetic susceptibility and the EPR spectra were measured over the temperature ranges 1.8-300 and 3-300 K, respectively. The magnetic moment was found to increase with decreasing temperature to reach a maximum of 2.60 mu(B) per one copper atom at ca. 10 K and was found, subsequently, to diminish slightly at lower temperatures owing to zero-field and Zeeman splitting of the S = 2 ground state. The temperature dependence of the magnetic susceptibility was fitted to the spin Hamiltonian H = J(ab)S(a)S(b) + J(bc)S(b)S(c), + J(cd)S(c)S(d), + J(ad)S(a)S(d) J(ac)S(a)S(c) + J(bd)S(b)S(d) with the exchange integrals J(ab) = J(bc), = J(cd) = J(ad) = -65(3) cm(-1) and J(ac) = J(bd) = + 1(3) cm(-1). High-field, high-frequency (95-380 GHz) EPR spectra due to an S = 2 ground state were simulated with g(x) = 2.138(1), g(y) = 2.142(1), g(z) = 2.067(1), D = -0.3529(3) cm(-1), and E = -0.0469(8) cm(-1). Calculations based on the X-ray structure indicate a negligible contribution of the magnetic dipole-dipole interactions to the zfs parameters D and E. A discussion of the isotropic and anisotropic exchange interactions and their effect on the zfs parameters is also given.",
author = "E.A. Buvaylo and V.N. Kokozay and O.Y. Vassilyeva and Brian Skelton and J. Jezierska and L.C. Brunel and A. Ozarowski",
year = "2005",
doi = "10.1021/ic049044p",
language = "English",
volume = "44",
pages = "206--216",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "2",

}

High-frequency, high-field EPR; magnetic susceptibility; and X-ray studies on a ferromagnetic heterometallic complex of diethanolamine (H2L), [Cu4(NH3)4(HL)4][CdBr4]Br2·3dmf·H2O. / Buvaylo, E.A.; Kokozay, V.N.; Vassilyeva, O.Y.; Skelton, Brian; Jezierska, J.; Brunel, L.C.; Ozarowski, A.

In: Inorganic Chemistry, Vol. 44, No. 2, 2005, p. 206-216.

Research output: Contribution to journalArticle

TY - JOUR

T1 - High-frequency, high-field EPR; magnetic susceptibility; and X-ray studies on a ferromagnetic heterometallic complex of diethanolamine (H2L), [Cu4(NH3)4(HL)4][CdBr4]Br2·3dmf·H2O

AU - Buvaylo, E.A.

AU - Kokozay, V.N.

AU - Vassilyeva, O.Y.

AU - Skelton, Brian

AU - Jezierska, J.

AU - Brunel, L.C.

AU - Ozarowski, A.

PY - 2005

Y1 - 2005

N2 - The novel heterometallic complex [Cu-4(NH3)(4)(HL)(4)][CdBr4]Br-2.3dmf.H2O has been prepared in the reaction of zerovalent copper with cadmium oxide in the air-exposed solution of ammonium bromide and diethanolamine (H2L) in dimethylformamide (dmf). The compound is monoclinic, with space group P2(1)/c, a = 14.876(3) Angstrom, b = 33.018-(6) Angstrom, c = 11.437(2) Angstrom, beta = 108.182(3)degrees, and Z = 4. The crystal lattice consists of [CU4(NH3)(4)(HL)(4)](4+) cations, [CdBr4](2-), Br- anions, and uncoordinated dmf and water molecules. In the cation, four independent Cu atoms occupy vertexes of a distorted tetrahedron with bridged (CuCu)-Cu-... distances in the range 3.127(2)-3.333(3) Angstrom and other (CuCu)-Cu-... separations being 3.445(3)-3.503(2) Angstrom. The magnetic susceptibility and the EPR spectra were measured over the temperature ranges 1.8-300 and 3-300 K, respectively. The magnetic moment was found to increase with decreasing temperature to reach a maximum of 2.60 mu(B) per one copper atom at ca. 10 K and was found, subsequently, to diminish slightly at lower temperatures owing to zero-field and Zeeman splitting of the S = 2 ground state. The temperature dependence of the magnetic susceptibility was fitted to the spin Hamiltonian H = J(ab)S(a)S(b) + J(bc)S(b)S(c), + J(cd)S(c)S(d), + J(ad)S(a)S(d) J(ac)S(a)S(c) + J(bd)S(b)S(d) with the exchange integrals J(ab) = J(bc), = J(cd) = J(ad) = -65(3) cm(-1) and J(ac) = J(bd) = + 1(3) cm(-1). High-field, high-frequency (95-380 GHz) EPR spectra due to an S = 2 ground state were simulated with g(x) = 2.138(1), g(y) = 2.142(1), g(z) = 2.067(1), D = -0.3529(3) cm(-1), and E = -0.0469(8) cm(-1). Calculations based on the X-ray structure indicate a negligible contribution of the magnetic dipole-dipole interactions to the zfs parameters D and E. A discussion of the isotropic and anisotropic exchange interactions and their effect on the zfs parameters is also given.

AB - The novel heterometallic complex [Cu-4(NH3)(4)(HL)(4)][CdBr4]Br-2.3dmf.H2O has been prepared in the reaction of zerovalent copper with cadmium oxide in the air-exposed solution of ammonium bromide and diethanolamine (H2L) in dimethylformamide (dmf). The compound is monoclinic, with space group P2(1)/c, a = 14.876(3) Angstrom, b = 33.018-(6) Angstrom, c = 11.437(2) Angstrom, beta = 108.182(3)degrees, and Z = 4. The crystal lattice consists of [CU4(NH3)(4)(HL)(4)](4+) cations, [CdBr4](2-), Br- anions, and uncoordinated dmf and water molecules. In the cation, four independent Cu atoms occupy vertexes of a distorted tetrahedron with bridged (CuCu)-Cu-... distances in the range 3.127(2)-3.333(3) Angstrom and other (CuCu)-Cu-... separations being 3.445(3)-3.503(2) Angstrom. The magnetic susceptibility and the EPR spectra were measured over the temperature ranges 1.8-300 and 3-300 K, respectively. The magnetic moment was found to increase with decreasing temperature to reach a maximum of 2.60 mu(B) per one copper atom at ca. 10 K and was found, subsequently, to diminish slightly at lower temperatures owing to zero-field and Zeeman splitting of the S = 2 ground state. The temperature dependence of the magnetic susceptibility was fitted to the spin Hamiltonian H = J(ab)S(a)S(b) + J(bc)S(b)S(c), + J(cd)S(c)S(d), + J(ad)S(a)S(d) J(ac)S(a)S(c) + J(bd)S(b)S(d) with the exchange integrals J(ab) = J(bc), = J(cd) = J(ad) = -65(3) cm(-1) and J(ac) = J(bd) = + 1(3) cm(-1). High-field, high-frequency (95-380 GHz) EPR spectra due to an S = 2 ground state were simulated with g(x) = 2.138(1), g(y) = 2.142(1), g(z) = 2.067(1), D = -0.3529(3) cm(-1), and E = -0.0469(8) cm(-1). Calculations based on the X-ray structure indicate a negligible contribution of the magnetic dipole-dipole interactions to the zfs parameters D and E. A discussion of the isotropic and anisotropic exchange interactions and their effect on the zfs parameters is also given.

U2 - 10.1021/ic049044p

DO - 10.1021/ic049044p

M3 - Article

VL - 44

SP - 206

EP - 216

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 2

ER -