Magnetic Anisotropy in Divalent Lanthanide Compounds

Zhang, Weibing; Muhtadi, Almas; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

doi:10.1002/anie.202003399

Cited by 35 publications

(46 citation statements)

References 59 publications

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“…The divalent lanthanoid ions also exhibit significant magnetic anisotropy, however these have not been not very well explored as SMMs because of their relative instability [35] . A recent ab initio study by Ungur and Chibotaru assessed the potential for divalent lanthanoids to show SMM behavior, remarking that lanthanoid(II) compounds possess the potential for blocking the magnetization at equally high temperatures, or even exceeding those of top performing lanthanoid(III) SMMs [36] . Research into Ln‐SMMs based on divalent lanthanoid ions therefore presents a new avenue for exploration.…”

Section: Fundamentalsmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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The development of molecular materials with novel functionality offers promise for technological innovation. Switchable molecules that incorporate redox‐active components are enticing candidate compounds due to their potential for electronic manipulation. Lanthanoid metals are most prevalent in their trivalent state and usually redox‐activity in lanthanoid complexes is restricted to the ligand. The unique electronic and physical properties of lanthanoid ions have been exploited for various applications, including in magnetic and luminescent materials as well as in catalysis. Lanthanoid complexes are also promising for applications reliant on switchability, where the physical properties can be modulated by varying the oxidation state of a coordinated ligand. Lanthanoid‐based redox activity is also possible, encompassing both divalent and tetravalent metal oxidation states. Thus, utilization of redox‐active lanthanoid metals offers an attractive opportunity to further expand the capabilities of molecular materials. This review surveys both ligand and lanthanoid centered redox‐activity in pre‐existing molecular systems, including tuning of lanthanoid magnetic and photophysical properties by modulating the redox states of coordinated ligands. Ultimately the combination of redox‐activity at both ligands and metal centers in the same molecule can afford novel electronic structures and physical properties, including multiconfigurational electronic states and valence tautomerism. Further targeted exploration of these features is clearly warranted, both to enhance understanding of the underlying fundamental chemistry, and for the generation of a potentially important new class of molecular material.

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Section: Fundamentalsmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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“…Theu seful qualitative static model reported by Rinehart and Long predicts that f 13 elements have aprolate shape [28] of the electron density and therefore require equatorial coordi-…”

Section: Resultsmentioning

confidence: 99%

“…Recently,s ome of us reported the first divalent lanthanide coordination complex exhibiting as low magnetic relaxation under aweak DC field. [19c] Theneed for this small DC field is typical in f 13 compounds. [20] In this article,w e extend this concept to the use of large typical organometallic ligands with rare occurrences in the divalent state.W ereport ahighly reducing divalent thulium sandwich complex behaving as aSingle Molecule Magnet in zero DC field.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, if ligand orbitals are involved in this picture, energy states with intermediate valence emerge [11] . More importantly, the modulation of the redox state of lanthanide compounds brings very interesting additional features such as higher magnetic moments [12] and larger magnetic anisotropy than those of the trivalent congeners [13] . However, there are also important drawbacks in the use of such compounds for SMMs because of their high reducing power, which reinforce the need for new accessible syntheses and stability studies.…”

Section: Introductionmentioning

confidence: 99%

“…We have been studying complexes containing divalent thulium [9,19] for several years for the principal reason that Tm II is very reactive and useful in single-electron transfer reactions but also because it is isoelectronic to Yb III , [9] with a4 f 13 configuration. Ther esulting one-hole electronic structure may simplify the spectroscopic features as af irst approximation.…”

Section: Introductionmentioning

confidence: 99%

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Bis‐Cyclooctatetraenyl Thulium(II): Highly Reducing Lanthanide Sandwich Single‐Molecule Magnets

et al. 2021

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Divalent lanthanide organometallics are well‐known highly reducing compounds usually used for single electron transfer reactivity and small molecule activation. Thus, their very reactive nature prevented for many years the study of their physical properties, such as magnetic studies on a reliable basis. Herein, the access to rare organometallic sandwich compounds of TmII with the cyclooctatetraenyl (Cot) ligand impacts on the use of divalent organolanthanide compounds as an additional strategy for the design of performing Single Molecule Magnets (SMM). The first divalent thulium sandwich complex with f13 configuration behaving as a single‐molecule magnet in absence of DC field is highlighted.

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The Impact of Lattice Distortions on the Magnetic Stability of Single Atoms: Dy and Ho on BaO(100)

Sorokin

Pivetta

Bellini

et al. 2023

Adv Funct Materials

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X‐ray magnetic circular dichroism, atomic multiplet simulations, and density functional theory calculations are employed to identify criteria for the optimum combination of supporting alkaline earth oxide and adsorption site maximizing the spin lifetimes of lanthanide single‐atom magnets. Dy and Ho atoms adsorbed on BaO(100) thin films on Pt(100) are characterized and compared with previous results for the same two elements on MgO/Ag(100). Dy shows hysteresis in magnetic fields up to ≈3.5 T and long spin lifetime, exceeding 300 s at 2.5 K and 0.5 T. Dy displays superior magnetic stability on the bridge site than on the top‐O site. Surprisingly, Ho shows paramagnetism, as opposed to its long spin lifetime on MgO. These differences originate from the local surface distortions induced by the adatoms. On MgO, minimal distortions involve only the closest O atoms, while, on BaO, they affect both the closest anions and cations. This trend reflects the decrease of the lattice energy along the series of the alkaline earth oxides, going from MgO to BaO. This study represents a step ahead in the understanding of the factors determining the spin dynamics of surface‐adsorbed single‐atom magnets in order to achieve their operation as qubits and memories.

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Magnetic Anisotropy in Divalent Lanthanide Compounds

Cited by 35 publications

References 59 publications

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Bis‐Cyclooctatetraenyl Thulium(II): Highly Reducing Lanthanide Sandwich Single‐Molecule Magnets

The Impact of Lattice Distortions on the Magnetic Stability of Single Atoms: Dy and Ho on BaO(100)

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