Magnetic Anisotropy in Divalent Lanthanide Compounds

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

doi:10.1002/ange.202003399

Cited by 5 publications

(2 citation statements)

References 59 publications

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“…[35] Ar ecent ab initio study by Ungur and Chibotaru assessed the potentialf or divalent lanthanoidst os how SMM behavior,r emarking that lanthanoid(II) compounds possess the potential for blocking the magnetization ate quallyh igh temperatures,o re ven exceeding those of top performing lanthanoid(III) SMMs. [36] Research into Ln-SMMs based on divalent lanthanoid ions therefore presents anew avenue for exploration.…”

Section: Magnetic Propertiesmentioning

confidence: 99%

“…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%

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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: Magnetic Propertiesmentioning

confidence: 99%

Section: Fundamentalsmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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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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Ln₂(SeO₃)₂(SO₄)(H₂O)₂ (Ln=Sm, Dy, Yb): A Mixed‐Ligand Pathway to New Lanthanide(III) Multifunctional Materials Featuring Nonlinear Optical and Magnetic Anisotropy Properties

et al. 2022

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Bottom‐up assembly of optically nonlinear and magnetically anisotropic lanthanide materials involving precisely placed spin carriers and optimized metal‐ligand coordination offers a potential route to developing electronic architectures for coherent radiation generation and spin‐based technologies, but the chemical design historically has been extremely hard to achieve. To address this, we developed a worthwhile avenue for creating new noncentrosymmetric chiral Ln3+ materials Ln2(SeO3)2(SO4)(H2O)2 (Ln=Sm, Dy, Yb) by mixed‐ligand design. The materials exhibit phase‐matching nonlinear optical responses, elucidating the feasibility of the heteroanionic strategy. Ln2(SeO3)2(SO4)(H2O)2 displays paramagnetic property with strong magnetic anisotropy facilitated by large spin‐orbit coupling. This study demonstrates a new chemical pathway for creating previously unknown polar chiral magnets with multiple functionalities.

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Magnetic Anisotropy in Divalent Lanthanide Compounds

Cited by 5 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

Ln₂(SeO₃)₂(SO₄)(H₂O)₂ (Ln=Sm, Dy, Yb): A Mixed‐Ligand Pathway to New Lanthanide(III) Multifunctional Materials Featuring Nonlinear Optical and Magnetic Anisotropy Properties

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Magnetic Anisotropy in Divalent Lanthanide Compounds

Cited by 5 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

Ln2(SeO3)2(SO4)(H2O)2 (Ln=Sm, Dy, Yb): A Mixed‐Ligand Pathway to New Lanthanide(III) Multifunctional Materials Featuring Nonlinear Optical and Magnetic Anisotropy Properties

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Ln₂(SeO₃)₂(SO₄)(H₂O)₂ (Ln=Sm, Dy, Yb): A Mixed‐Ligand Pathway to New Lanthanide(III) Multifunctional Materials Featuring Nonlinear Optical and Magnetic Anisotropy Properties