Interactions between well-isolated Dy3+ ions considerably contribute to the demagnetization of a mononuclear
Andrey V Gavrikov1, Andrey B Ilyukhin1, Mikhail E Buzoverov1
1Kurnakov Institute of General and Inorganic Chemistry RAS, Leninskii prosp., 31, Moscow, Russia. penguin1990@yandex.ru.
Abstract:
A series of new mononuclear square antiprismatic complexes comprising acetylacetonate (acac-), pyrazine-2-carboxylate (PyrCOO-) and 1,10-phenanthroline (phen) ligands, namely, [Ln(acac)2(PyrCOO)(phen)] (Ln is Dy-Yb, Y; 1-5, 6), was prepared and studied. These complexes are new examples of extremely scarcely studied eight-coordinated tetra-chelate complexes comprising β-diketonate and carboxylate ligands. Complexes 1, 3 and 5 exhibit pronounced slowdown of demagnetization, with corresponding pathways additionally validated by ab initio calculations. In particular, complex 1 exhibits zero-field relaxation with a Δeff/kB of 149 K, while the application of an optimal DC field (1500 Oe) enhances the Δeff/kB value to 265 K. Thus, although the quantum tunneling of magnetization (QTM) contributes to zero-field relaxation of complex 1, this complex is among the most efficient zero-field Dy-based SMMs formed by β-diketonate and/or carboxylate ligands. Moreover, the Δeff/kB value of 1 under the optimal field is the highest among the related complexes. Interestingly, the Dy-Dy magnetic interactions have a considerable effect on the SMM performance of 1, despite on the spatial (>8 Å) separation of Dy3+ ions isolated by coats of bulky diamagnetic ligands.
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