Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of CuII(bdmmp)2(H2O), PrIIICuII(bdmmp)(bdmmpH)(μ-OH)(hfacac)3, [LaIIICuII(bdmmp)(bdmmpH)(μ-OH)(O2CCF 3)3] ...

Liqin Chen, Steven R. Breeze, Roger Rousseau, Suning Wang, Laurence K. Thompson

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Abstract

Full title: Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of CuII(bdmmp)2(H2O), PrIIICuII(bdmmp)(bdmmpH)(μ-OH)(hfacac)3, [LaIIICuII(bdmmp)(bdmmpH)(μ-OH)(O2CCF 3)3]2, and CuII 4(bdmmp)24-O)(O 2CCF3)4, (bdmmpH = 2,6-bis[(dimethylamino)methyl]-4-methylphenol; hfacac = hexafluoroacetylacetonato). The syntheses of polynuclear copper(II)-lanthanide(III) complexes using the 2,6-bis[(dimethylamino)methyl]-4-methylphenolato ligand (bdmmp) have been investigated. The reaction of Cu(OCH3)2 with 2 equiv of bdmmpH in THF yields a mononuclear copper complex Cu(bdmmp)2(H2O) (1), which subsequently reacts with 1 equiv of Pr(hfacac)3 or La(O2CCF3)3 (hfacac = hexafluoroacetylacetonato) to produce two heteronuclear complexes PrIII-CuII(bdmmp)(bdmmpH)(OH)(hfacac)3 (2) and [LaIIICuII(bdmmp)(bdmmpH)(OH)(O2CCF 3)3]2 (3). The reaction of Cu(OCH3)2, Cu(O2CCF3)2, bdmmpH, and H2O in a 1:1:1:0.5 ratio in THF yields a tetranuclear copper complex Cu4(bdmmp)24-O)(O2CCF 3)4 (4). The structures of compounds 1-4 have been determined by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic crystal space group C2/c, with a = 17.443-(8) Å, b = 9.510(3) Å, c = 20.459(9) Å, β = 122.89(3)°, V = 2849(2) Å3, and Z = 4. Compound 2 crystallizes in the monoclinic space group P21/n, with a = 14.304(8) Å, b = 19.122(6) Å, c = 20.059(4) Å, β = 100.21(3)°, V = 5399(3) Å3, and Z = 4. Compound 3 crystallizes in the triclinic space group P1, with a = 13.106(6) Å, b = 17.15(1) Å, c = 11.152(6) Å, α = 97.14(4)°, β = 108.48(4)°, γ = 93.85(4)°, V = 2343(2) Å3, and Z = 1. Compound 4 crystallizes in the orthorhombic space group P212121, with a = 18.408(7) Å, b = 22.88(1) Å, c = 10.598(5) Å, V = 4464(2) Å3, and Z = 4. The magnetic properties of these compounds have been examined by variable-temperature magnetic susceptibility measurements. The magnetism of compound 2 is dominated by the paramagnetism of the Pr(III) ion, while the magnetism of 4 is dominated by antiferromagnetic exchanges of the Cu(II) ions with J1 = -101 cm-1, J2 = -101 cm-1, J3 = -45 cm-1, J4 = 3 cm-1, and g = 2.02. UV-vis spectroscopic studies revealed that compound 1 has an intense ligand → metal charge transfer band at λ = 427 nm. Molecular orbital analysis on the electronic structure of 1 by extended Hückel MO methods indicates that this absorption band is mainly due to the transitions of the π orbitals of the phenoxy ligand to the singly occupied dx2-y2 orbital of the copper ion.

Original languageEnglish
Pages (from-to)454-465
Number of pages12
JournalInorganic Chemistry
Volume34
Issue number2
Publication statusPublished - 1995

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Amino Alcohols
Lanthanoid Series Elements
Copper
alcohols
Ligands
copper
ligands
synthesis
Magnetism
Ions
Paramagnetism
orbitals
ions
paramagnetism
Molecular orbitals
Electron transitions
Magnetic susceptibility
X ray diffraction analysis
Electronic structure
Charge transfer

ASJC Scopus subject areas

  • Inorganic Chemistry

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@article{66a6778359b84b45ad9f9ed9d1728749,
title = "Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of CuII(bdmmp)2(H2O), PrIIICuII(bdmmp)(bdmmpH)(μ-OH)(hfacac)3, [LaIIICuII(bdmmp)(bdmmpH)(μ-OH)(O2CCF 3)3] ...",
abstract = "Full title: Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of CuII(bdmmp)2(H2O), PrIIICuII(bdmmp)(bdmmpH)(μ-OH)(hfacac)3, [LaIIICuII(bdmmp)(bdmmpH)(μ-OH)(O2CCF 3)3]2, and CuII 4(bdmmp)2(μ4-O)(O 2CCF3)4, (bdmmpH = 2,6-bis[(dimethylamino)methyl]-4-methylphenol; hfacac = hexafluoroacetylacetonato). The syntheses of polynuclear copper(II)-lanthanide(III) complexes using the 2,6-bis[(dimethylamino)methyl]-4-methylphenolato ligand (bdmmp) have been investigated. The reaction of Cu(OCH3)2 with 2 equiv of bdmmpH in THF yields a mononuclear copper complex Cu(bdmmp)2(H2O) (1), which subsequently reacts with 1 equiv of Pr(hfacac)3 or La(O2CCF3)3 (hfacac = hexafluoroacetylacetonato) to produce two heteronuclear complexes PrIII-CuII(bdmmp)(bdmmpH)(OH)(hfacac)3 (2) and [LaIIICuII(bdmmp)(bdmmpH)(OH)(O2CCF 3)3]2 (3). The reaction of Cu(OCH3)2, Cu(O2CCF3)2, bdmmpH, and H2O in a 1:1:1:0.5 ratio in THF yields a tetranuclear copper complex Cu4(bdmmp)2(μ4-O)(O2CCF 3)4 (4). The structures of compounds 1-4 have been determined by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic crystal space group C2/c, with a = 17.443-(8) {\AA}, b = 9.510(3) {\AA}, c = 20.459(9) {\AA}, β = 122.89(3)°, V = 2849(2) {\AA}3, and Z = 4. Compound 2 crystallizes in the monoclinic space group P21/n, with a = 14.304(8) {\AA}, b = 19.122(6) {\AA}, c = 20.059(4) {\AA}, β = 100.21(3)°, V = 5399(3) {\AA}3, and Z = 4. Compound 3 crystallizes in the triclinic space group P1, with a = 13.106(6) {\AA}, b = 17.15(1) {\AA}, c = 11.152(6) {\AA}, α = 97.14(4)°, β = 108.48(4)°, γ = 93.85(4)°, V = 2343(2) {\AA}3, and Z = 1. Compound 4 crystallizes in the orthorhombic space group P212121, with a = 18.408(7) {\AA}, b = 22.88(1) {\AA}, c = 10.598(5) {\AA}, V = 4464(2) {\AA}3, and Z = 4. The magnetic properties of these compounds have been examined by variable-temperature magnetic susceptibility measurements. The magnetism of compound 2 is dominated by the paramagnetism of the Pr(III) ion, while the magnetism of 4 is dominated by antiferromagnetic exchanges of the Cu(II) ions with J1 = -101 cm-1, J2 = -101 cm-1, J3 = -45 cm-1, J4 = 3 cm-1, and g = 2.02. UV-vis spectroscopic studies revealed that compound 1 has an intense ligand → metal charge transfer band at λ = 427 nm. Molecular orbital analysis on the electronic structure of 1 by extended H{\"u}ckel MO methods indicates that this absorption band is mainly due to the transitions of the π orbitals of the phenoxy ligand to the singly occupied dx2-y2 orbital of the copper ion.",
author = "Liqin Chen and Breeze, {Steven R.} and Roger Rousseau and Suning Wang and Thompson, {Laurence K.}",
year = "1995",
language = "English",
volume = "34",
pages = "454--465",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of CuII(bdmmp)2(H2O), PrIIICuII(bdmmp)(bdmmpH)(μ-OH)(hfacac)3, [LaIIICuII(bdmmp)(bdmmpH)(μ-OH)(O2CCF 3)3] ...

AU - Chen, Liqin

AU - Breeze, Steven R.

AU - Rousseau, Roger

AU - Wang, Suning

AU - Thompson, Laurence K.

PY - 1995

Y1 - 1995

N2 - Full title: Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of CuII(bdmmp)2(H2O), PrIIICuII(bdmmp)(bdmmpH)(μ-OH)(hfacac)3, [LaIIICuII(bdmmp)(bdmmpH)(μ-OH)(O2CCF 3)3]2, and CuII 4(bdmmp)2(μ4-O)(O 2CCF3)4, (bdmmpH = 2,6-bis[(dimethylamino)methyl]-4-methylphenol; hfacac = hexafluoroacetylacetonato). The syntheses of polynuclear copper(II)-lanthanide(III) complexes using the 2,6-bis[(dimethylamino)methyl]-4-methylphenolato ligand (bdmmp) have been investigated. The reaction of Cu(OCH3)2 with 2 equiv of bdmmpH in THF yields a mononuclear copper complex Cu(bdmmp)2(H2O) (1), which subsequently reacts with 1 equiv of Pr(hfacac)3 or La(O2CCF3)3 (hfacac = hexafluoroacetylacetonato) to produce two heteronuclear complexes PrIII-CuII(bdmmp)(bdmmpH)(OH)(hfacac)3 (2) and [LaIIICuII(bdmmp)(bdmmpH)(OH)(O2CCF 3)3]2 (3). The reaction of Cu(OCH3)2, Cu(O2CCF3)2, bdmmpH, and H2O in a 1:1:1:0.5 ratio in THF yields a tetranuclear copper complex Cu4(bdmmp)2(μ4-O)(O2CCF 3)4 (4). The structures of compounds 1-4 have been determined by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic crystal space group C2/c, with a = 17.443-(8) Å, b = 9.510(3) Å, c = 20.459(9) Å, β = 122.89(3)°, V = 2849(2) Å3, and Z = 4. Compound 2 crystallizes in the monoclinic space group P21/n, with a = 14.304(8) Å, b = 19.122(6) Å, c = 20.059(4) Å, β = 100.21(3)°, V = 5399(3) Å3, and Z = 4. Compound 3 crystallizes in the triclinic space group P1, with a = 13.106(6) Å, b = 17.15(1) Å, c = 11.152(6) Å, α = 97.14(4)°, β = 108.48(4)°, γ = 93.85(4)°, V = 2343(2) Å3, and Z = 1. Compound 4 crystallizes in the orthorhombic space group P212121, with a = 18.408(7) Å, b = 22.88(1) Å, c = 10.598(5) Å, V = 4464(2) Å3, and Z = 4. The magnetic properties of these compounds have been examined by variable-temperature magnetic susceptibility measurements. The magnetism of compound 2 is dominated by the paramagnetism of the Pr(III) ion, while the magnetism of 4 is dominated by antiferromagnetic exchanges of the Cu(II) ions with J1 = -101 cm-1, J2 = -101 cm-1, J3 = -45 cm-1, J4 = 3 cm-1, and g = 2.02. UV-vis spectroscopic studies revealed that compound 1 has an intense ligand → metal charge transfer band at λ = 427 nm. Molecular orbital analysis on the electronic structure of 1 by extended Hückel MO methods indicates that this absorption band is mainly due to the transitions of the π orbitals of the phenoxy ligand to the singly occupied dx2-y2 orbital of the copper ion.

AB - Full title: Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of CuII(bdmmp)2(H2O), PrIIICuII(bdmmp)(bdmmpH)(μ-OH)(hfacac)3, [LaIIICuII(bdmmp)(bdmmpH)(μ-OH)(O2CCF 3)3]2, and CuII 4(bdmmp)2(μ4-O)(O 2CCF3)4, (bdmmpH = 2,6-bis[(dimethylamino)methyl]-4-methylphenol; hfacac = hexafluoroacetylacetonato). The syntheses of polynuclear copper(II)-lanthanide(III) complexes using the 2,6-bis[(dimethylamino)methyl]-4-methylphenolato ligand (bdmmp) have been investigated. The reaction of Cu(OCH3)2 with 2 equiv of bdmmpH in THF yields a mononuclear copper complex Cu(bdmmp)2(H2O) (1), which subsequently reacts with 1 equiv of Pr(hfacac)3 or La(O2CCF3)3 (hfacac = hexafluoroacetylacetonato) to produce two heteronuclear complexes PrIII-CuII(bdmmp)(bdmmpH)(OH)(hfacac)3 (2) and [LaIIICuII(bdmmp)(bdmmpH)(OH)(O2CCF 3)3]2 (3). The reaction of Cu(OCH3)2, Cu(O2CCF3)2, bdmmpH, and H2O in a 1:1:1:0.5 ratio in THF yields a tetranuclear copper complex Cu4(bdmmp)2(μ4-O)(O2CCF 3)4 (4). The structures of compounds 1-4 have been determined by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic crystal space group C2/c, with a = 17.443-(8) Å, b = 9.510(3) Å, c = 20.459(9) Å, β = 122.89(3)°, V = 2849(2) Å3, and Z = 4. Compound 2 crystallizes in the monoclinic space group P21/n, with a = 14.304(8) Å, b = 19.122(6) Å, c = 20.059(4) Å, β = 100.21(3)°, V = 5399(3) Å3, and Z = 4. Compound 3 crystallizes in the triclinic space group P1, with a = 13.106(6) Å, b = 17.15(1) Å, c = 11.152(6) Å, α = 97.14(4)°, β = 108.48(4)°, γ = 93.85(4)°, V = 2343(2) Å3, and Z = 1. Compound 4 crystallizes in the orthorhombic space group P212121, with a = 18.408(7) Å, b = 22.88(1) Å, c = 10.598(5) Å, V = 4464(2) Å3, and Z = 4. The magnetic properties of these compounds have been examined by variable-temperature magnetic susceptibility measurements. The magnetism of compound 2 is dominated by the paramagnetism of the Pr(III) ion, while the magnetism of 4 is dominated by antiferromagnetic exchanges of the Cu(II) ions with J1 = -101 cm-1, J2 = -101 cm-1, J3 = -45 cm-1, J4 = 3 cm-1, and g = 2.02. UV-vis spectroscopic studies revealed that compound 1 has an intense ligand → metal charge transfer band at λ = 427 nm. Molecular orbital analysis on the electronic structure of 1 by extended Hückel MO methods indicates that this absorption band is mainly due to the transitions of the π orbitals of the phenoxy ligand to the singly occupied dx2-y2 orbital of the copper ion.

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M3 - Article

VL - 34

SP - 454

EP - 465

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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