A Dy4 single-molecule magnet and its Gd(<scp>iii</scp>), Tb(<scp>iii</scp>), Ho(<scp>iii</scp>), and Er(<scp>iii</scp>) analogues encapsulated by an 8-hydroxyquinoline Schiff base derivative and β-diketonate coligand

Gao, Hong-Ling; Zhou, Xiao-Pu; Bi, Yan-Xia; Shen, Hai-Yun; Wang, Wenmin; Wang, Nini; Chang, Ye; Zhang, Ruxia; Cui, Jian-Zhong

doi:10.1039/c7dt00118e

Cited by 53 publications

(11 citation statements)

References 88 publications

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“…The largest −Δ S m value of 21.88 J kg –1 K –1 occurs at 2 K when Δ H is 5 T, this value is smaller than the value of 31.43 J kg –1 K –1 calculated using the formula, −Δ S m = nR ln(2 S + 1) ( n = 4, S = 7/2 and the R value is 8.314 J mol –1 K –1 ), owing to the antiferromagnetic interaction among Gd 3+ ions in 2 . This value is larger in magnetic refrigeration molecule materials, and comparable with those of other Gd 4 cluster complexes when Δ H is 5 T. − …”

Section: Resultssupporting

confidence: 59%

Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands: Single-molecule Magnet Behavior and Magnetic Entropy Change

Liu

Hao

2022

ACS Omega

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It is challenging to use achiral ligands to spontaneously construct chiral molecular magnets. In this work, two new Ln 4 cluster complexes based on N , N ′-(1,3-propanediyl)bis[ N -[1,1-bis(hydroxymethyl)-2-hydroxyethyl]amine] (H 6 L) have been assembled, which are crystallized in a chiral space group due to the asymmetric distribution of acetate (OAc – ) groups and hexafluoroacetylacetonate (F 6 acac – ) groups on both sides of the parallelogram-like Ln 4 core. Complex 1 , [Dy 4 (H 3 L) 2 (OAc) 3 (F 6 acac) 3 ]·5MeOH·2H 2 O, exhibits single-molecule magnet properties at the zero field with the U eff / k value of 48.4 K; notably, besides the Orbach process, the Raman process is also prominent for the magnetic relaxation of 1 . Complex 2 , [Gd 4 (H 3 L) 2 (OAc) 3 (F 6 acac) 3 ]·4MeOH·2.5H 2 O, displays a large magnetocaloric effect, whose largest −Δ S m value is 21.88 J kg –1 K –1 (when T = 2 K and Δ H = 5 T); it thus can be utilized as a good magnetic refrigeration molecular material.

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Section: Resultssupporting

confidence: 59%

Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands: Single-molecule Magnet Behavior and Magnetic Entropy Change

Liu

Hao

2022

ACS Omega

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“…The absence of slow magnetic relaxation for Zn 2 Dy 4 ·5H 2 O clearly contrasts with the magnetic behavior observed for many nonlinear Dy 4 complexes with oxygen bridges, which usually behave as SMMs. − This fact is remarkable, especially if we take into account that it has been demonstrated, both theoretically and experimentally, that the introduction of Zn II typically increases the anisotropic energy barrier of lanthanoid complexes. − The absence of magnetic relaxation for this complex may be due to a possible exchange coupling between Dy III ions. Unfortunately, we have not been able to obtain a similar Gd 3+ derivative, which could bring some light to this issue.…”

Section: Resultsmentioning

confidence: 88%

Tb₂, Dy₂, and Zn₂Dy₄ Complexes Showing the Unusual Versatility of a Hydrazone Ligand toward Lanthanoid Ions: a Structural and Magnetic Study

et al. 2018

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Three dinuclear complexes, [Tb(Hdaps)(CHOH)(HO)](Cl) (TbCl), [Dy(Hdaps)(Cl)(CHOH)(HO)]Cl (DyCl), and [Dy(Hdaps)(HO)](CFSO) (DyCFSO), as well as the heterohexanuclear compound [ZnDy(daps)(Hdaps)(Cl)(OH)(CHOH)(HO)] (ZnDy) (Hdaps: 2,6-bis(1-salicyloylhydrazonoethyl)pyridine), which crystallize with different lattice molecules, show their hexa- or heptadentate hydrazone ligands acting with hitherto unknown μ-κ:κ, μ-κ:κ:κ, μ-κ:κ:κ:κ, or μ-κ:κ:κ:κ bridging modes. The single X-ray crystal structures of the dinuclear complexes show nine-coordinated N O environments for lanthanoid atoms in TbCl and DyCFSO, with distorted geometries, between spherical capped square antiprism and muffin-like, while the dysprosium atoms in DyCl are eight-coordinated, with distorted triangular dodecahedron geometries. In the case of ZnDy, both eight-coordinated, O and O Cl, as well as nine-coordinated N O environments coexist in the crystal structure, with biaugmented trigonal prism, triangular dodecahedron, and muffin-like pseudogeometries. The magnetic study of all the complexes shows that none of the pure samples behaves as a single molecular magnet (SMM) and that the quantum tunnel cannot be removed by dilution of any of the dinuclear complexes, but except in diluted [YDy(Hdaps)(Cl)(HO)]Cl (DyCl@Y), behaves as a weak field induced SMM. The heterohexanuclear ZnDy complex also lacks slow relaxation of the magnetization.

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“…The decrease of χ M T upon the temperature cooling can be attributed to the thermal depopulation of the m J levels of the ground state of the Dy(III) ions and/or the possible antiferromagnetic interactions between the metal centers, which is in agreement with reported similar Dy(III) complexes. 51,52 For 3, the χ M T curve gradual decrease to 51.26 cm 3 K mol −1 at 12 K then increased rapidly to a maximum of 54.75 cm 3 K mol −1 at 1.8 K. The increase of χ M T at low temperature suggests the presence of ferromagnetic interactions between the Dy(III) ions.…”

Section: Resultsmentioning

confidence: 93%

Tuning the Magnetic Interactions in Dy(III)₄ Single-Molecule Magnets

et al. 2018

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The study of mononuclear lanthanide-based systems, where the observed single-molecule magnets (SMMs) properties originate from the local description of the magnetic properties of the lanthanide ion, has been widely investigated through the literature. The case of polynuclear SMMs becomes more challenging both experimentally and theoretically due to the complexity of such architectures involving interactions between the magnetic centers. Many efforts have been focused on the understanding of the nature of these interactions and their effects on the SMM properties. In this work, a series of three structurally related tetranuclear dysprosium(III) SMMs, namely, [Dy(L)(OH)(DMF)(NO)]·2(DMF)·(HO) (1), [Dy(L)(OH)(DMF)(tfaa)]·2(CHCN) (2), and [Dy(L)(OH)(DMF)(acac)]·2(DMF) (3) (HL = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol, Htfaa = trifluoroacetylactone, Hacac = acetylacetonate), has been synthesized and investigated. By a fine-tuning of the ligands on the changeable coordination sites in these Dy(III) SMMs, the intramolecular magnetic interactions can be modified, switching from antiferromagnetic (for 1 and 2) to ferromagnetic (for 3). Ab initio calculations support these statements. In addition, the formation of 1 has been analyzed by ESI-MS analysis of the reaction mixture, indicating rather quick and high-yield formation of the [Dy] framework in solution. The combination of experimental work and ab initio calculations offers further insight into the relationship between structures and magnetic properties and sheds light on how to tune magnetic interactions in future polynuclear dysprosium complexes.

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A Dy4 single-molecule magnet and its Gd(iii), Tb(iii), Ho(iii), and Er(iii) analogues encapsulated by an 8-hydroxyquinoline Schiff base derivative and β-diketonate coligand

Cited by 53 publications

References 88 publications

Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands: Single-molecule Magnet Behavior and Magnetic Entropy Change

Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands: Single-molecule Magnet Behavior and Magnetic Entropy Change

Tb₂, Dy₂, and Zn₂Dy₄ Complexes Showing the Unusual Versatility of a Hydrazone Ligand toward Lanthanoid Ions: a Structural and Magnetic Study

Tuning the Magnetic Interactions in Dy(III)₄ Single-Molecule Magnets

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A Dy4 single-molecule magnet and its Gd(iii), Tb(iii), Ho(iii), and Er(iii) analogues encapsulated by an 8-hydroxyquinoline Schiff base derivative and β-diketonate coligand

Cited by 53 publications

References 88 publications

Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands: Single-molecule Magnet Behavior and Magnetic Entropy Change

Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands: Single-molecule Magnet Behavior and Magnetic Entropy Change

Tb2, Dy2, and Zn2Dy4 Complexes Showing the Unusual Versatility of a Hydrazone Ligand toward Lanthanoid Ions: a Structural and Magnetic Study

Tuning the Magnetic Interactions in Dy(III)4 Single-Molecule Magnets

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Tb₂, Dy₂, and Zn₂Dy₄ Complexes Showing the Unusual Versatility of a Hydrazone Ligand toward Lanthanoid Ions: a Structural and Magnetic Study

Tuning the Magnetic Interactions in Dy(III)₄ Single-Molecule Magnets