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

• DOI: 10.1021/jacs.3c12427
• Publication Date: 2024-01-29T08:24:45Z
• Authors: Jack Emerson-King; Gemma K. Gransbury; George F. S. Whit...; Iñigo J. Vitorica...; Mathieu Rouzières; Rodolphe Clérac; Nicholas F. Chilton; David P. Mills
• Keywords: 01 natural sciences; 0104 chemical sciences

The isolation of formally two-coordinate lanthanide (Ln) complexes is synthetically challenging, due to predominantly ionic Ln bonding regimes favoring high coordination numbers. In 2014 some of us 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 = 924(17) 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.