Mononuclear Fe(III) and tetranuclear [Fe(III)Gd(III)]2 complexes with a Schiff-base ligand derived from the o-vanillin: Synthesis, crystal structures and magnetic properties |
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Authors: | Masood SarwarAugustin M Madalan Franceso LloretMiguel Julve Marius Andruh |
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Institution: | a Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava Rosie 23, 020464 Bucharest, Romania b Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol), C/ Catedrático José Beltrán n° 2, 46980 Paterna (Valencia), Spain |
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Abstract: | The mononuclear high-spin iron(III) complexes Fe(3-MeOsalpn)Cl(H2O)] (1) and Fe(3-MeOsalpn)(NCS)(H2O)]·0.5CH3CN (2) and the tetranuclear oxo-bridged compound {Fe(3-MeOsalpn)Gd(NO3)3}2(μ-O)]·CH3CN (3) 3-MeOsalpn2− = N,N′-propylenebis(3-methoxysalicylideneiminate)] have been prepared and magneto-structurally characterised. The iron(III) ion in 1 and 2 is six-coordinated in a somewhat distorted octahedral surrounding with the two phenolate-oxygens and two imine-nitrogens from the Schiff-base building the equatorial plane and a water (1 and 2) and a chloro (1)/thiocyanate-nitrogen (2) in the axial positions. The neutral mononuclear units of 1 and 2 are assembled into centrosymmetric dinuclear motifs through hydrogen bonds between the axially coordinated water molecule of one iron centre and methoxy-oxygen atoms from the Schiff-base of the adjacent iron atom. The values of the intradimer metal-metal distance within the supramolecular dimers are 4.930 (1) and 4.878 Å (2). The tetranuclear of 3 can be described as two {FeIII(3-MeOsalpn)} units connected through an oxo-bridge, each one hosting a GdIII(NO3)3] entity in the outer cavity defined by the two phenolate- and two methoxy-oxygen atoms. The values of the intramolecular Fe?Fe and Fe?Gd distances in 3 are 3.502 and 3.606 Å, respectively. The analysis of the magnetic data of 1-3 in the temperature range 1.9-300 K shows the occurrence of weak intermolecular antiferromagnetic interactions in 1 and 2 J = −0.76 (1) and −0.75 cm−1 (2) with the Hamiltonian defined as H = −JSFe1·SFe1] whereas two intramolecular antiferromagnetic interactions coexist in 3, one very strong between the two iron(III) ions (J1) through the oxo bridge and the other much weaker between the iron(III) and the Gd(III) ions (J2) across the double phenoxo oxygens J1 = −275 cm−1 and J2 = −3.25 cm−1, the Hamiltonian being defined as H=-J1SFe1·SFe1′-J2(SFe1·SGd1+SFe1′·SGd1′)]. These values are analysed in the light of the structural data and compared with those of related systems. |
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Keywords: | Iron(III) complexes Gadolinium(III) complexes Heterometallic complexes Schiff-base complexes Magnetic properties Supramolecular dimers |
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