Syntheses, crystal structures and magnetic properties of a series of defect-dicubane tetranickel(II) systems with variable, mixed and interchangeable µ3-core ligands

Shuvayan Roy, Hazel A Sparkes, Sasankasekhar Mohanta

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Abstract

The article describes syntheses, crystal structures and magnetic properties of six defective dicubane type NiII4 clusters of compositions [NiII4(HL1)23-X)21,1-N3)21,3carboxylato)2]·nH2O (1, X = OMe, carboxylato = o-benzoylbenzoato, n = 0; 2, X = {(OMe)0.83(N3)0.17}, carboxylato = phenyl acetato, n = 2; 3, X = {(OMe)0.80(N3)0.20}, carboxylato = salicylato, n = 0; 4, X = OH, carboxylato = o-benzoylbenzoato, n = 2; 5, X = {(N3)0.58(OMe)0.42}, carboxylato = o-benzoylbenzoato, n = 2) and [NiII4(HL1)21,1,1N3)21,1-N3)2(N3)2(H2O)2]·4DMF (6), where H2L1 is 2-Formyl-6-{(2-hydroxy-1,1-dimethylethylimino)-methyl}-4-ethyl-phenol, and this is the partially hydrolysed product of initially employed ligand H3L, 2,6-Bis-{(2-hydroxy-1,1-dimethyl-ethylimino)-methyl}-4-ethylphenol. Each of the two compartments of each [HL1]‒ in 1‒6 is occupied by a NiII ion, to form a NiII2 fragment. The common bridges between the two metal ions in a dinuclear fragment are μ-phenoxo of [HL1]‒ and one μ3-core ligand (methoxo/hydroxo/mixture of methoxo and μ1,1,1-azido) while the additional bridge in 1‒5 is a μ1,3-carboxylato. Two dinuclear fragments are interlinked by two μ1,1-azido and two μ3-core ligands. Interestingly, the μ3-methoxo compound 1 and the μ3-hydroxo compound 4 are interconvertible in both ways as the function of the solvents. Variable-temperature and variable-field magnetic studies reveal overall ferromagnetic interactions in each of 1‒6.
Original languageEnglish
Number of pages13
JournalEuropean Journal of Inorganic Chemistry
Early online date18 Oct 2019
DOIs
Publication statusE-pub ahead of print - 18 Oct 2019

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