A Low‐Symmetry Dysprosium Metallocene Single‐Molecule Magnet with a High Anisotropy Barrier

Pugh, Thomas; Chilton, Nicholas F.; Layfield, Richard A.

doi:10.1002/anie.201604346

Cited by 173 publications

(101 citation statements)

References 37 publications

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“…[10] The key magneto-structural correlation arising from this work is that the [Cp] -ligands provide a dominant axial crystal field that enhances the magnetic anisotropy of Dy 3+ , whereas the heteroatom donor ligands moderate the anisotropy, thus limiting Ueff and enabling zero-field QTM. [11] The logical conclusion from our studies is therefore that removing the equatorial ligands to give a discrete metallocenium cation of the type [(Cp)2Dy] + should dramatically increase the anisotropy barrier and the blocking temperature, TB.…”

Section: A Dysprosium Metallocene Single-molecule Magnet Functioning mentioning

confidence: 79%

A Dysprosium Metallocene Single‐Molecule Magnet Functioning at the Axial Limit

et al. 2017

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Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] (1Dy Cpttt=1,2,4‐tri(tert‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth metallocenium cation [(Cpttt)2Dy]+ (2Dy) as a salt of the non‐coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low‐lying Kramers doublets correspond to a well‐defined MJ value, with no significant mixing even in the higher doublets.

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Section: A Dysprosium Metallocene Single-molecule Magnet Functioning mentioning

confidence: 79%

A Dysprosium Metallocene Single‐Molecule Magnet Functioning at the Axial Limit

et al. 2017

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“…3%.T he value of t 0 is of the correct order of magnitude expected for Orbach relaxation over al arge barrier [15] and the values of C and n are within the range commonly observed for the Raman process for Dy III SMMs. [10,16] The U eff observed is only relevant to magnetic…”

Section: Angewandte Chemiementioning

confidence: 99%

On Approaching the Limit of Molecular Magnetic Anisotropy: A Near‐Perfect Pentagonal Bipyramidal Dysprosium(III) Single‐Molecule Magnet

et al. 2016

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We report a monometallic dysprosium complex, [Dy(O Bu) (py) ][BPh ] (5), that shows the largest effective energy barrier to magnetic relaxation of U =1815(1) K. The massive magnetic anisotropy is due to bis-trans-disposed tert-butoxide ligands with weak equatorial pyridine donors, approaching proposed schemes for high-temperature single-molecule magnets (SMMs). The blocking temperature, T , is 14 K, defined by zero-field-cooled magnetization experiments, and is the largest for any monometallic complex and equal with the current record for [Tb N {N(SiMe ) } (THF) ].

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“…In fact, high‐performance lanthanide SMMs possess highly symmetric electrostatic environments that induce strong stabilization of the magnetic ground state . A striking illustration of the latter concept is given by the Ln–phthalocyanine (LnPc) systems, where the organic ligands impose a strict D 4 d site symmetry to the lanthanide ion and dramatically improve its magnetic properties when compared with a distorted coordination environment .…”

Section: Introductionmentioning

confidence: 99%

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Huang

Garcia

Badiane

et al. 2018

Chemistry A European J

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We report the study of a Dy-based metal-organic framework (MOF) with unprecedented magnetic properties. The compound is made of nine-coordinated Dy magnetic building blocks (MBBs) with poor intrinsic single-molecule magnet behavior. However, the MOF architecture constrains the MBBs in a one-dimensional structure that induces a ferromagnetic coupling between them. Overall, the material shows a magnetic slow relaxation in absence of external static field and a hysteretic behavior at 0.5 K. Low-temperature magnetic studies, diamagnetic doping, and ab initio calculations highlight the crucial role played by the Dy-Dy ferromagnetic interaction. Overall, we report an original magnetic object at the frontier between single-chain magnets and single-molecule magnets that host intrachain couplings that cancel quantum tunneling between the MBBs. This compound is evidence that a bottom-up approach through MOF design can induce spontaneous organization of MBBs able to produce remarkable molecular magnetic materials.

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A Low‐Symmetry Dysprosium Metallocene Single‐Molecule Magnet with a High Anisotropy Barrier

Cited by 173 publications

References 37 publications

A Dysprosium Metallocene Single‐Molecule Magnet Functioning at the Axial Limit

A Dysprosium Metallocene Single‐Molecule Magnet Functioning at the Axial Limit

On Approaching the Limit of Molecular Magnetic Anisotropy: A Near‐Perfect Pentagonal Bipyramidal Dysprosium(III) Single‐Molecule Magnet

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

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