Novel Co5 and Ni4 Metal Complexes and Ferromagnets by the Combination of 2-Pyridyl Oximes with Polycarboxylic Ligands

2-吡啶肟与多羧酸配体结合制备新型 Co5 和 Ni4 金属配合物和铁磁体

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作者:Foteini Dimakopoulou, Costantinos G Efthymiou, Ciaran O'Malley, Andreas Kourtellaris, Eleni Moushi, Anastasios Tasiopooulos, Spyros P Perlepes, Patrick McArdle, Ernesto Costa-Villén, Julia Mayans, Constantina Papatriantafyllopoulou

Abstract

The use of 2-pyridyl oximes in metal complexes chemistry has been extensively investigated in the last few decades as a fruitful source of species with interesting magnetic properties. In this work, the initial combination of pyridine-2-amidoxime (pyaoxH2) and 2-methyl pyridyl ketoxime (mpkoH) with isonicotinic acid (HINA) and 3,5-pyrazole dicarboxylic acid (H3pdc) has provided access to three new compounds, [Ni4(INA)2(pyaox)2(pyaoxH)2(DMF)2] (1), [Co5(mpko)6(mpkoH)2(OMe)2(H2O)](ClO4)6 (2), and [Co5(OH)(Hpdc)5(H2pdc)] (3). 1 displays a square-planar metal topology, being the first example that bears simultaneously HINA and pyaoxH2 in their neutral or ionic form. The neighbouring Ni4 units in 1 are held together through strong intermolecular hydrogen bonding interactions, forming a three-dimensional supramolecular framework. 2 and 3 are mixed-valent Co4IIICoII and Co2IIICoII3 compounds with a bowtie and trigonal bipyramidal metal topology, accordingly. Direct current and alternate current magnetic susceptibility studies revealed that the exchange interactions between the NiII ions in 1 are ferromagnetic (J = 1.79(4) cm-1), while 2 exhibits weak AC signals in the presence of a magnetic field. The syntheses, crystal structures, and magnetic properties of 1-3 are discussed in detail.

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