Abstract
Tetranuclear hetero-metal MnIII2NiII2 complexes, [Mn2Ni2(L)4(OAc)2] (1) and [Mn2Ni2(L)4(NO3)2] (2) [H2L = N-(2-hydroxymethylphenyl)-5,6-benzosalicylideneimine], have been synthesized and characterized by X-ray crystal structure analyses, infrared spectra, and elemental analyses. The structure analyses revealed that the complexes have a defective double-cubane metal core connected by μ3-alkoxo bridges. Complexes consist of two bis-μ-alkoxo bridged MnIIINiII heteronuclear units making a dimer-of-dimers structure. The double-cubane cores are significantly distorted due to an effect of syn–syn mode acetato or nitrato bridges. Magnetic measurements indicate that weak antiferromagnetic interactions (Mn-Ni = −0.66 ~ −4.19 cm–1) are dominant in the hetero-metal core.
Highlights
Molecular magnetism of discrete complexes with a cubane-based metal core structure have been extensively studied over the past few decades [1,2,3,4]
The key focal points of the investigation on such molecular magnetism are the following: (i) understanding of the basic correlation of spin coupling and molecular structure based on the analyses of the concerned orbitals [5]; (ii) application of the correlations in polynuclear systems that have several exchange pathways [6,7,8]; (iii) development of magnetic materials that behave like single molecule magnets (SMMs) [1,2,3,4,9]
The cubane core structures are commonly obtained with homo-metal complexes, whereas double-cubane structures are often formed by hetero-metal or mixed-valence complexes
Summary
Molecular magnetism of discrete complexes with a cubane-based metal core structure have been extensively studied over the past few decades [1,2,3,4]. We have reported that the Schiff base tridentate ligand, N-(2-hydroxymethylphenyl) salicylideneimine (H2L1-H) [14] and its derivatives, can be used to produce cubane-like tetranuclear complexes via simple one-pot reactions [15,16,17]. As expected, these ligands gave hetero-metal or mixed-valence complexes characterized by a double-cubane metal core structure with a large high-spin ground state; such complexes included, for instance, MnIII2NiII2 (ST = 6) and CoIII2CoII2 (ST = 3) systems [16,17]. We report here the syntheses, structures and magnetic properties of tetranuclear hetero-metal MnIII2NiII2 complexes
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