Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Crystal Structures and Magnetic Properties of Copper(II) Hexafluoroacetylacetonate Complexes with hnn and hin and Manganese(II) Hexafluoroacetylacetonate Complex with hin (hnn = 4,4,5,5-Tetramethylimidazolin-1-oxyl 3-Oxide; hin = 4,4,5,5-Tetramethylimidazolin-1-oxyl)
Tomoaki IseTakayuki IshidaTakashi Nogami
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2002 Volume 75 Issue 11 Pages 2463-2468

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Abstract

We report here the structures and magnetic properties of hnn and hin complexes with copper(II) and manganese(II) hexafluoroacetylacetonates, [{Cu(hfac)2(H2O)}2(μ-hnn)] (1), [Cu(hfac)2(hin)2] (2), and [Mn(hfac)2(hin)2] (3). X-ray crystallographic analysis of 1 revealed that 1 was a dinuclear complex containing an hnn bridge. Magnetic measurements of 1 indicate the presence of intramolecular ferromagnetic coupling between copper and radical spins. The data were analyzed as a metal-radical-metal three-spin system, giving 2J/k = +16.2 K (H = −2J(S1S2 + S2S3)). The ferromagnetic interaction can be explained in terms of the axial coordination of the hnn nitrogen to Cu(II). Complexes 2 and 3 were revealed to be isomorphous mononuclear complexes possessing two hin ligands. Although the molecules have a radical-metal-radical system, the magnetic data of 3 could not be analysed only with intramolecular interactions. Strong intermolecular antiferromagnetic interactions (2|J|/k >> 300 K) were suggested among the hin ligands because the interatomic O···N distances (2.41–2.51 Å) were shorter than the sum of the van der Waals radii for 2 and 3. These strong interactions are successfully introduced to metal-radical hybrid systems owing to the choice of small ligands, although the complexes do not possess polymeric networks.

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© 2002 The Chemical Society of Japan
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