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)(O2CCF3)3]2, and CuII4(bdmmp)24-O)(O2CCF3)4, (bdmmpH = 2,6-Bis[(dimethylamino)methyl]-4-methylphenol; hfacac = Hexafluoroacetylacetonato)

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

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Abstract

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)(O2CCF3)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)(O2CCF3)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 γ = 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
DOIs
Publication statusPublished - Jan 1 1995

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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