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Article Dans Une Revue Journal of the American Chemical Society Année : 2024

Isolation of a Bent Dysprosium Bis(amide) Single-Molecule Magnet

Jack Emerson-King
Gemma K Gransbury
George F S Whitehead
Iñigo J Vitorica-Yrezabal
  • Fonction : Auteur
Rodolphe Clérac
Nicholas F Chilton
David P Mills

Résumé

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(Si i Pr 3) 2 } 2 ] + could provide a single-molecule magnet (SMM) with an energy barrier to magnetic reversal (U eff) of up to 2600 K, a 3-fold increase of the record U eff 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(Si i Pr 3) 2 } 2 ][Al{OC(CF 3) 3 } 4 ] (1-Dy), together with the diamagnetic yttrium analogue. We find U eff = 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 U eff 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.
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Dates et versions

hal-04445224 , version 1 (07-02-2024)

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Paternité

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Jack Emerson-King, Gemma K Gransbury, George F S Whitehead, Iñigo J Vitorica-Yrezabal, Mathieu Rouzières, et al.. Isolation of a Bent Dysprosium Bis(amide) Single-Molecule Magnet. Journal of the American Chemical Society, 2024, 146 (5), pp.3331-3342. ⟨10.1021/jacs.3c12427⟩. ⟨hal-04445224⟩

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