Interactions between well-isolated Dy3+ ions considerably contribute to the demagnetization of a mononuclear acetylacetonate–pyrazinate complex

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.

Graphical abstract: Interactions between well-isolated Dy3+ ions considerably contribute to the demagnetization of a mononuclear acetylacetonate–pyrazinate complex

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Article information

Article type
Paper
Submitted
28 Mar 2025
Accepted
07 May 2025
First published
09 May 2025

Dalton Trans., 2025, Advance Article

Interactions between well-isolated Dy3+ ions considerably contribute to the demagnetization of a mononuclear acetylacetonate–pyrazinate complex

A. V. Gavrikov, A. B. Ilyukhin, M. E. Buzoverov, K. A. Babeshkin, E. N. Timokhina, N. N. Breslavskaya, P. N. Vasilyev and N. N. Efimov, Dalton Trans., 2025, Advance Article , DOI: 10.1039/D5DT00749F

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