2021
DOI: 10.1002/chem.202100085
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Mononuclear Dysprosium Alkoxide and Aryloxide Single‐Molecule Magnets

Abstract: Recent studies have shown that mononuclear lanthanide (Ln) complexes can be high‐performing single‐molecule magnets (SMMs). Recently, there has been an influx of mononuclear Ln alkoxide and aryloxide SMMs, which have provided the necessary geometrical control to improve SMM properties and to allow the intricate relaxation dynamics of Ln SMMs to be studied in detail. Here non‐aqueous Ln alkoxide and aryloxide chemistry applied to the synthesis of low‐coordinate mononuclear Ln SMMs are reviewed. The focus is on … Show more

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Cited by 93 publications
(68 citation statements)
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References 156 publications
(560 reference statements)
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“…3 SMMs containing a low coordination number (CN) Dy(III) centre with axial crystal fields (CF) have their most magnetic m J states stabilised, enhancing the energy barrier to magnetic reversal (U eff ). 4,5 Weakly coordinating ligands (or no ligands) in the equatorial plane can reduce the transverse CF components that are responsible for relaxation via quantum tunnelling of magnetisation (QTM). 1,2,6 Magnetic relaxation in SMMs involves multiple pathways; it is necessary to improve our understanding of these processes in order to rationally target SMMs with longer relaxation times.…”
mentioning
confidence: 99%
See 1 more Smart Citation
“…3 SMMs containing a low coordination number (CN) Dy(III) centre with axial crystal fields (CF) have their most magnetic m J states stabilised, enhancing the energy barrier to magnetic reversal (U eff ). 4,5 Weakly coordinating ligands (or no ligands) in the equatorial plane can reduce the transverse CF components that are responsible for relaxation via quantum tunnelling of magnetisation (QTM). 1,2,6 Magnetic relaxation in SMMs involves multiple pathways; it is necessary to improve our understanding of these processes in order to rationally target SMMs with longer relaxation times.…”
mentioning
confidence: 99%
“…6 Bulky alkoxide and aryloxide ligands have proven useful in synthesising low-coordinate Dy SMMs with appropriate CF requirements. 5 In recent years, axial CN7 Dy alkoxide SMMs with pentagonal bipyramidal geometries have been studied extensively. [7][8][9][10] Only a handful of Dy alkoxide or aryloxide SMMs with CN o 6 have been reported to date.…”
mentioning
confidence: 99%
“…Indeed, the Dy−H distances range from 2.29 to 2.41 Å, whereas the Dy−O are sensitively longer (2.413–2.457 Å). For comparison in benchmark SMMs with a PB geometry, the bond lengths ratio between axial and equatorial ligands dL ax /dL eq is usually less than 0.90, [8f, i] pointing out a strong axiality. In contrast, such ratio is larger than 0.95 for 1 .…”
Section: Methodsmentioning
confidence: 99%
“…Lanthanide ions are playing a crucial role in the design of Single-Molecule Magnets (SMM) thanks to their strong magnetic anisotropy and high magnetic moment [1][2][3][4][5][6][7][8][9][10]. The ideal adequacy between the nature of the used lanthanide and crystal field environment allowed chemists to elaborate SMMs displaying magnetic memory at a temperature up to 80 K [11,12].…”
Section: Introductionmentioning
confidence: 99%