Academic Journal
Isolation of a bent dysprosium bis(amide) single-molecule magnet
| العنوان: | Isolation of a bent dysprosium bis(amide) single-molecule magnet |
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| المؤلفون: | Emerson-King, Jack, Gransbury, Gemma K., Whitehead, George F. S., Vitorica-Yrezabal, Inigo J., Rouzières, Mathieu, Clérac, Rodolphe, Chilton, Nicholas F., Mills, David P. |
| المصدر: | Emerson-King , J , Gransbury , G K , Whitehead , G F S , Vitorica-Yrezabal , I J , Rouzières , M , Clérac , R , Chilton , N F & Mills , D P 2024 , ' Isolation of a bent dysprosium bis(amide) single-molecule magnet ' , Journal of the American Chemical Society . https://doi.org/10.1021/jacs.3c12427 |
| سنة النشر: | 2024 |
| المجموعة: | The University of Manchester: Research Explorer - Publications |
| الوصف: | 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 threefold 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 analog. 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. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| Relation: | https://research.manchester.ac.uk/en/publications/8a87ff54-8510-4666-92c9-9d5c1dc5fb5a |
| DOI: | 10.1021/jacs.3c12427 |
| الاتاحة: | https://research.manchester.ac.uk/en/publications/8a87ff54-8510-4666-92c9-9d5c1dc5fb5a https://doi.org/10.1021/jacs.3c12427 |
| Rights: | info:eu-repo/semantics/openAccess |
| رقم الانضمام: | edsbas.4FB51A20 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/jacs.3c12427 |
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