Two New Diphenoxo-Bridged Discrete Dinuclear CuIIGdIII Compounds with Cyclic Diimino Moieties: Syntheses, Structures, and Magnetic Properties

doi:10.1002/ejic.200400858

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Title:	Two New Diphenoxo-Bridged Discrete Dinuclear CuIIGdIII Compounds with Cyclic Diimino Moieties: Syntheses, Structures, and Magnetic Properties
Authors:	魏和祥;Wei, Ho-hsiang;Koner, Rajesh;Lee, Gene-Hsiang;Wang, Yu;Mohant, Sasankasekhar
Contributors:	淡江大學化學學系
Keywords:	Magnetic properties;Compartmental ligands;Gadolinium(III);Ferromagnetic;Heterometallic complexes
Date:	2005-04-21
Issue Date:	2009-12-01
Publisher:	Wiley-Blackwell
Abstract:	Two Schiff base compartmental ligands, H2L1 and H2L2, derived from the condensation of 3-ethoxysalicylaldehyde with 1,2-diaminocyclohexane and orthophenylenediamine, respectively, have been utilized to isolate two diphenoxo-bridged discrete dinuclear CuIIGdIII complexes, [CuII(H2O)L1GdIII(NO3)3] (3) and [CuIIL2GdIII(NO3)3] (4). This is the first report on the 3d-4f compounds derived from compartmental Schiff base ligands with cyclic diamines. The compounds 3 and 4 crystallize in the triclinic Pequation image and orthorhombic Pna2(1) space groups, respectively, with the following unit cell parameters – 3: a = 8.8713(2) Å, b = 12.8399(3) Å, c = 14.0067(3) Å, α = 80.6649(5)°, β = 77.4059(5)°, γ = 76.8879(5)°, and Z = 2; 4: a = 9.2210(1) Å, b = 16.5407(2) Å, c = 19.9248(4) Å, and Z = 4. Structural analysis reveals that both are discrete dinuclear complexes. In 3, one water molecule is coordinated to the copper(II) ion to result in a square-pyramidal coordination geometry, while the geometry of the coppe(II) center in 4 is square planar. In both complexes, the gadolinium(III) center has an O10 coordination environment. In contrast to expectation, although the N2O2 cavity affords a better planar environment for the copper(II) center in 4, the bridging moiety in complex 3 is more planar than that in 4 or in most of the previously reported examples (the dihedral angle between two CuO2Gd planes: 2.1° for 3 and 7.1° for 4). Variable-temperature and variable-field magnetic measurements reveal that the metal centers in both the complexes are ferromagnetically coupled (J values: 6.3 cm–1 for 3 and 5.4 cm–1 for 4; H = –2JSCu·SGd). Interestingly, complex 3 exhibits strongest ferromagnetic interaction among the related compounds.
Relation:	European journal of inorganic chemistry 2005(8), pp.1500-1505
DOI:	10.1002/ejic.200400858
Appears in Collections:	[Graduate Institute & Department of Chemistry] Journal Article

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