Polynuclear copper-lanthanide complexes with amino alcohol ligands. Syntheses, structures, and magnetic and spectroscopic studies of Cu{sup II}(bdmmp){sub 2}(H{sub 2}O), Pr{sup III}Cu{sup II}(bdmmp)(bdmmpH)({mu}-OH)(hfacac){sub 3}, [La{sup III}Cu{sup II}(bdmmp)(bdmmpH)({mu}-OH)(O{sub 2}CCF{sub 3}){sub 3}]{sub 2}, and Cu{sup II}{sub 4}(bdmmp){sub 2}({mu}{sub 4}-O)(O{sub 2}CCF{sub 3}){sub 4}, (bdmmpH = 2,6-bis[(dimethylamino)methyl]-4-methylphenol; hfacac = hexafluoroacetylacetonato)
- Univ. of Windsor, Ontario (Canada)
- Memorial Univ. of Newfoundland, St. John`s (Canada)
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(OCH{sub 3}){sub 2} with 2 equiv of bdmmpH in THF yields a mononuclear copper complex Cu(bdmmp){sub 2}(H{sub 2}O) (1), which subsequently reacts with 1 equiv of Pr(hfacac){sub 3} or La(O{sub 2}CCF{sub 3}){sub 3} (hfacac = hexafluoroacetylacetonato) to produce two heteronuclear complexes Pr{sup III}-Cu{sup II}(bdmmp)(bdmmpH)(OH)(hfacac){sub 3} (2) and [La{sup III}Cu{sup II}(bdmmp)(bdmmpH)(OH)(O{sub 2}CCF{sub 3}){sub 3}]{sub 2} (3). The reaction of Cu{sub 4}(bdmmp){sub 2}({mu}{sub 4}-O)(O{sub 2}CCF{sub 3}){sub 4} (4). The structures of compounds 1-4 have been determined by single-crystal X-ray diffraction analysis. 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 J{sub 1} = -101 cm{sup {minus}1}, J{sub 2} = -101 cm{sup {minus}1}, J{sub 3} = -45 cm{sup {minus}1}, J{sub 4} = 3 cm{sup {minus}1}, and g = 2.02. UV-vis spectroscopic studies revealed that compound 1 has an intense ligand {yields} metal charge transfer band at {lambda} = 427 nm. Molecular orbital analysis on the electronic structure of 1 by extended Hueckel MO methods indicates that this absorption band is mainly due to the transitions of the {pi} orbitals of the phenoxy ligand to the singly occupied d{sub x{sup 2}-y{sup 2}} orbital of the copper ion.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 75654
- Journal Information:
- Inorganic Chemistry, Vol. 34, Issue 2; Other Information: PBD: 18 Jan 1995
- Country of Publication:
- United States
- Language:
- English
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