Isolation of a bent dysprosium bis(amide) single-molecule magnet

Jack Emerson-King, Gemma K. Gransbury, George F. S. Whitehead, Inigo J. Vitorica-Yrezabal, Mathieu Rouzières, Rodolphe Clérac, Nicholas F. Chilton, David P. Mills

Research output: Contribution to journalArticlepeer-review

Abstract

The isolation of formally two-coordinate lanthanide (Ln) complexes is synthetically challenging, due to predominantly ionic Ln bonding regimes favoring high coordination numbers. In 2015 it was predicted that a near-linear dysprosium bis(amide) cation [Dy{N(SiiPr3)2}2]+could provide a single-molecule magnet (SMM) with an energy barrier to magnetic reversal (Ueff) of up to 2600 K, a threefold increase of the record Ueff for a Dy SMM at the time; this work showed a potential route to SMMs that can provide high-density data storage at higher temperatures. However, synthetic routes to a Dy complex containing only two
monodentate ligands have not previously been realized. Here we report the synthesis of the target bent dysprosium bis(amide) complex, [Dy{N(SiiPr3)2}2][Al{OC(CF3)3}4] (1-Dy), together with the diamagnetic yttrium analog. We find Ueff = 950 ± 30 K for 1-Dy, which is much lower than the predicted values for idealized linear two-coordinate Dy(III) cations. Ab initio calculations of the static electronic structure disagree with the experimentally-determined height of the Ueff barrier, thus magnetic relaxation is faster than expected based on magnetic anisotropy alone. We propose that this is due to enhanced spin-phonon coupling arising from the flexibility of the Dy coordination sphere, in accord with ligand vibrations being of equal importance to magnetic anisotropy in the design of high-temperature SMMs.
Original languageEnglish
JournalJournal of the American Chemical Society
Early online date29 Jan 2024
DOIs
Publication statusE-pub ahead of print - 29 Jan 2024

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