Bis-pyrazolone-based dysprosium(<scp>iii</scp>) complexes: zero-field single-molecule magnet behavior in the [2 × 2] grid DyIII4 cluster

Gebretsadik, Tesfay; Li, Xiao-Lei; Zhao, Chen; Yang, Qianqian; Tang, Jinkui

doi:10.1039/d2ce01067d

Cited by 9 publications

(6 citation statements)

References 60 publications

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“…However, the anisotropic energy barriers and magnetic relaxation times of cluster 2 are analyzed by thermal activation of the Orbach relaxation process ( τ = τ 0 exp( U eff / k B T )). 51–53 The fitting results show that under a zero DC field, the effective energy barrier and magnetic relaxation time of cluster 2 are U eff 9.7 (0.37) K and τ = 1.13 × 10 −5 s, respectively (Fig. S6d†).…”

Section: Resultsmentioning

confidence: 97%

Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

Huang

Wang

et al. 2023

CrystEngComm

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Section: Resultsmentioning

confidence: 97%

Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

Huang

Wang

et al. 2023

CrystEngComm

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“…As shown in Figure b, the Cole–Cole diagrams of complex (1) are relatively semicircular, and the fitted values are basically consistent with the generalized Debye model. The anisotropic energy barrier and magnetic relaxation time of complex (1) was analyzed by the Arrhenius equation (τ = τ 0 exp( U eff / k B T ), where τ 0 is the pre-exponential factor, U eff is the flip energy barrier, and k B is the Boltzmann constant). − The results show that under the optimal external DC fields, the effective energy barrier and magnetic relaxation time of complex (1) are U eff = 6.5 (0.30) K; τ 0 = 4.1 × 10 –5 s (Figure c, blue line). In addition, we also considered the Raman process ( CT n ).…”

Section: Resultsmentioning

confidence: 99%

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

Ai,

Li,

Zhu

et al. 2023

Crystal Growth & Design

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The potential docking spots in the structure of lanthanide complexes provide opportunities for subsequent synthetic modification or introduction of other metal centers. Usually, multidentate chelating ligands are used to construct lanthanide complexes, and multiple dense coordination sites tightly wrap the metal center; it is difficult to expose vacant coordination sites in a wide range. Herein, a series of lanthanide complexes with a potential docking spot were obtained by in situ Schiff base reaction via a solvothermal "one-pot" method, and their structures and molecular magnetic properties were explored. Specifically, DyCl 3 •6H 2 O, ovanillin, and 3-methoxysalicylaldehyde were reacted under solvothermal conditions at 100 °C to obtain a mononuclear dysprosium complex [Dy(L 1 ) 2 Cl 3 ] (1) with exposed N 2 O 4 coordination sites, and it is a field-induced single-molecule magnet (SMM). In addition, Ln(NO 3 ) 3 •6H 2 O 4-diethylaminosalicylaldehyde and 2,2-dimethyl-1,3-propanediamine reacted under solvothermal conditions at 80 °C, and five binuclear complexes, [Ln 2 (L 2 ) 3 (NO 3 ) 6 ]•3CH 3 CN (Ln = Dy (2), Tb (3), Ho (4), Er (5), and Gd (6)), with a large number of exposed N 4 O 4 coordination sites were obtained, which were mononuclear as independent units and connected by Schiff base ligands (L 2 ) 2− . It is worth noting that the maximum −ΔS m of complex (6) is 15.92 J kg −1 K −1 , higher than the commercially used magnetic refrigerant GGG (Gd 3 Gd 5 O 12 ; about 14.6 J kg −1 K −1 ), and complex (6) can be considered as a potential molecular-based material for magnetic refrigeration. Schiff base ligands with multidentate chelating coordination are usually used to construct lanthanide complexes. Their abundant and dense coordination sites can quickly capture metal centers to form clusters, but it is difficult to free up exposed coordination sites that can be used for structural modification.

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“…[62,63] This kind of relaxation can usually be suppressed by the application of dc field. [64,65] The optimized dc field was determined through the field-dependent ac susceptibility measurements (Figure S15), giving the optimized dc field of 500 Oe. After applying this dc field, frequency-and temperature-dependent χ" peaks were observed in the ac measurements (Figures 3 and S16), indicative of the field-induced single-molecule magnetic property.…”

Section: Dynamic Magnetic Properties Of Dy 2 and Dymentioning

confidence: 99%

The Assembly of Grid-type Lanthanide Cluster

Zhang

Guo

et al. 2022

Magnetochemistry

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A dicompartmental Schiff base ligand was synthesized and used for the assembly of a lanthanide grid-like complex. Dinuclear Dy2 and tetranuclear Dy4 complexes were isolated from the reaction of the ligand with different dysprosium salt. Single crystal X-ray diffractions show that the two DyIII ions in Dy2 are adopted in the N3O coordination pockets of the ligand and further coordinated by water molecules, whereas, for Dy4, the four DyIII ions are clamped by four ligands through their terminal N3O coordination pockets, forming a grid-type assembly. Magnetic studies reveal that complex Dy2 shows field-induced single-molecule magnetic behavior under 1000 Oe dc field, complex Dy4 shows fast relaxation under zero field and field-induced single-molecule magnet (SMM) behavior under 500 Oe. The difference in the magnetic relaxation is related to the various deprotonation of the ligand and distinct topology of the assemblies.

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Bis-pyrazolone-based dysprosium(iii) complexes: zero-field single-molecule magnet behavior in the [2 × 2] grid DyIII4 cluster

Abstract: We assembled two new Dy(III) compounds, namely, [Dy4(L1)4(OH)4]·2CH3OH (1) and [Dy2(L2)2(HL2)2(CH3CN)2]N(C2H5)3 (2) (where H2L1 and H2L2 are methyl-substituted and p-tolyl substituted ligands respectively) using a bis-pyrazolone carbohydrazide based multi-dentate hydrazone...

Cited by 9 publications

References 60 publications

Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

The Assembly of Grid-type Lanthanide Cluster

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