Investigating the effect of lanthanide radius and diamagnetic linkers on the framework of metallacrown complexes†
Abstract
By changing the stoichiometric ratios, the one-pot reaction of the glycinehydroxamic acid (H2glyha) ligand with copper(II) and lanthanide(III) salts in the presence of diamagnetic [Na2{Fe(CN)5(NO)}] led to two series of isostructural complexes, which can be designated as heterotrimetallic dimeric clusters [{LnCu5(glyha)5}{Fe(CN)5(NO)}(H2O)4]2·xNO3·yH2O (x = 2, y = 11 for La (1), x = 2, y = 11 for Pr (2), and x = 2, y = 11 for Nd (3)) and heterotetrametallic coordination polymers [Na{LnCu5(glyha)5}{Fe(CN)5(NO)}2(H2O)x·yH2O]n (x = 6, y = 4 for Sm (4), x = 6, y = 0 for Gd (5), x = 6, y = 4 for Tb (6), x = 5, y = 5 Dy (7), and x = 6, y = 4 for Ho (8)). Each molecular structure contains LnIII[15-metallacrown-5] nodes and diamagnetic [Fe(CN)5(NO)]2− linkers. The resulting products demonstrate diversified structural frameworks due to the radius effect of LnIII ions and different bridging fashions of diamagnetic [Fe(CN)5(NO)]2− linkers. An analysis of magnetic susceptibilities reveals that 7 exhibits ferromagnetic coupling between CuII and DyIII ions and field-induced SMM behavior.
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