Slow magnetic relaxation in a Dy<sub>3</sub> triangle and a bistriangular Dy<sub>6</sub> cluster

Wang, Wen; Shang, Tao; Wang, Juan; Yao, Binling; Li, Licun; Ma, Yue; Wang, Qing‐Lun; Zhang, Yuan‐Zhu; Zhang, Yi‐Quan; Zhao, Bin

doi:10.1039/d1dt03414f

Cited by 10 publications

(11 citation statements)

References 73 publications

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“…Dy2 is coordinated in square antiprism (Tables S5 and S7 and Figures S8 and S11) by seven O atoms and one N atom for 1 and eight O atoms for 2 . The coordination bonds (2.220(3)-2.507(6) Å) of Dy(III)–O/N agree well with reported values in literature studies. − Both (L 1 ) 3– in 1 and (HL 2 ) 3– in 2 present the same bridging mode of μ 4 -η 1 :η 1 :η 2 :η 4 with their two O alkoxy atoms behaving as μ 3 -bridges (Figures S9 and S12). Obviously, there is still one hydroxyl group being un-deprotonated and free from coordination for (HL 2 ) 3– ligands in 2 .…”

Section: Resultssupporting

confidence: 87%

Assembly Studies of Two Planar Dy₄ Single-Molecule Magnets

Chen

Zhang

et al. 2022

Crystal Growth & Design

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Two tetranuclear Dy(III) complexes formulated as [Dy4(L1)2(L′)4(EtOH)2(CH3CN)2(H2O)2]Cl2 (1) and [Dy4(HL2)2(L′)4(MeOH)6]Cl2·3MeOH·2CH3CN (2) were synthesized from the reactions of DyCl3·6H2O with the corresponding 2-hydroxy-1-naphthaldehyde Schiff bases under hydrothermal conditions (H3L1 = 2-methyl-2-((2′-hydroxynaphthalen-1′-yl)methyleneamino)propanediol, HL′ = 2-hydroxy-1-naphthaldehyde, and H4L2 = 2-(hydroxymethyl)-2-((2′-hydroxynaphthalen-1′-yl)methyleneamino)propanediol). The two Dy(III) complexes possess planar rhombus tetranuclear skeletons with different substitution groups on the Schiff base ligand. The magnetic investigation revealed field-induced single-molecule magnets for the two titled clusters. It suggests that both coordinated solvent molecules and substitution groups have a certain tuning effect on the single-molecule magnet performance. Their assembling processes were further investigated through time-dependent high-resolution electrospray ionization mass spectrometry, giving possible assembling mechanisms for the two titled single-molecule magnets.

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Section: Resultssupporting

confidence: 87%

Assembly Studies of Two Planar Dy₄ Single-Molecule Magnets

Chen

Zhang

et al. 2022

Crystal Growth & Design

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“…The triangular Dy 3 unit is less equilateral with Dy···Dy distances of 3.4871 (d Dy2–Dy3 ), 3.4987 (d Dy1–Dy2 ), and 3.567 Å (d Dy1–Dy3 ). The Dy–O and Dy–N bond lengths are in the range of 2.290–2.485 and 2.471–2.480 Å, respectively, matching with the corresponding values reported in the literature. − Four of the six trifluormethaneosulfonates involve in intramolecular hydrogen bonding with four μ 3 –OH – groups, while the remaining two participate in intramolecular hydrogen bonding with two coordinated ethanol molecules (Figure S7).…”

Section: Resultssupporting

confidence: 83%

“…The M−H curves show similar trends: a steep increase of the magnetization was observed in the low field interval while a slow increase at higher field until almost saturation to approach the largest value of 5.14, 25.81, and 30.65 Nβ at 7 T at 2 K, respectively. These numbers of three complexes are significantly lower than the theoretical saturation value for theoretical saturation values (the theoretical value should be 10 Nβ for one Dy(III) ion), 53,58 which supports the presence of significant magnetic anisotropy and/or possible low-lying excited states. In addition, the M versus H/T plots of Dy 1 , Dy 5, and Dy 6 at various temperatures cannot be superimposed into a single master curve, proving the non-negligible magnetic anisotropy (Figures S12−S14).…”

Section: ■ Experimental Sectionmentioning

confidence: 67%

Synthesis, Structure, and Magnetic Properties of Homometallic Mono-, Penta-, and Hexanuclear Dysprosium Complexes

Pan

et al. 2023

Crystal Growth & Design

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Regulation of the complex structure is greatly significant for the preparation of single-molecule magnets (SMMs). A Schiff base ligand, having suitably flexible coordination pockets, is usually designed to construct SMMs. In this text, three new homometallic complexes ([Dy(HL)2](NO3)·2H2O (Dy1 ), [Dy5(L)4(CH3CO2)6](CH3CO2)·6MeOH·H2O (Dy5 ), and [Dy6(L)2(L1)2(u3-OH)4(CF3SO3)6(EtOH)4]·2EtOH (Dy6 )) were synthesized based on a Schiff base ligand, 6,6′-dimethoxy-2,2′-[4,5-dimethyl-o-phenylenebis(nitrilomethylidyne)]-diphenol (H2L), which has an N2O2 pocket and a certain extent of steric hindrance. Their structures are characterized by single-crystal X-ray diffraction, and their magnetic properties are also explored. Complex Dy1 is a double-decker structure in which the Dy ion is sandwiched by two HL– ligands. Complex Dy5 displays a helical quadruple-decker structure which can be regarded as the structural extension of complex Dy1 but this is terminated by the coordination of acetate groups. Complex Dy6 is a centrosymmetric hexanuclear structure in which three Dy(III) ions construct an independent triangular plane. The new ligand L1 2– (H2L1 = 2-(hydroxymethyl)-6-methoxyphenol) in complex Dy6 is produced in situ from H2L under hydrothermal conditions. Magnetic studies on these complexes revealed that both Dy1 and Dy6 are typical SMMs, with a U eff/kB value of 38.4 K for Dy1 and 33.6 K for Dy6 , respectively, and complex Dy5 also shows SMM behavior under a zero dc field.

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“…The central [Dy 3 ] forms a triangular structure (Figure S9) bridged by a μ 3 -OH – and three μ 2 -OH – with the Dy–O–Dy bond angles of 105.40(18)° and 114.86(19)°, respectively. Similar Dy 3 triangle complexes have also been reported. ,,,− Each Dy(III) ion is seven-coordinate (Figure S10) and is surrounded by two phenol oxygen atoms of the L 2– ligand from [Zn II Cl(L)] − , three bridging oxygen atoms of OH – , one ethanol oxygen atom, and one chloride ion. The bond lengths of Dy–Cl are all 2.7535(16) Å, longer than the six Dy–O coordination bond lengths in the range of 2.220(3)–2.445(5) Å.…”

Section: Results and Discussionsupporting

confidence: 75%

Chiral Zn₃Ln₃ Hexanuclear Clusters of an Achiral Flexible Ligand

Liu

Zeng

et al. 2023

Inorg. Chem.

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Multifunctional single-molecule magnets (SMMs) have sparked great interest, but chiral SMMs obtained via spontaneous resolution are rarely reported. We synthesized a series of chiral trinuclear hepta-coordinate lanthanide complexes [ZnII 3LnIII 3] (1 for Dy, 2 for Tb, 3 for Gd, and 4 for Dy0.07Y0.93) using the achiral flexible ligand H2L (2,2′-[1,2-ethanediylbis[(ethylimino)methylene]]bis[3,5-dimethylphenol]). The complexes crystallize in the chiral P63 group space, and two enantiomers of different chirality are spontaneously resolved. Three [Zn(L)Cl]− anions utilize the two phenoxy oxygen atoms of each L2– to coordinate with three lanthanide ions, respectively, and the three hepta-coordinate D 5h lanthanide ions are arranged in a triangle. The chirality comes from the propeller arrangement of the peripheral three bidentate chelate L2– ligands like octahedral [M(AA)3] n+/– (M = transition metal ions; AA = bidentate chelate ligands, e.g., 2,2′-bipyridine, 1,10-phenathroline, ethylenediamine, acac– or oxalate). Complex 1 exhibits an AC susceptibility signal and is frequency-dependent, which is typical of SMMs. Complex 4, doped with a large amount of diamagnetic Y(III) in Dy(III), exhibits U eff = 48.3 K and τ0 = 4.4 × 10–8 s in experiments. Complex 2 shows circularly polarized luminescence and apparent photoluminescence, typical of the f–f transitions of Tb(III).

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Slow magnetic relaxation in a Dy₃ triangle and a bistriangular Dy₆ cluster

Cited by 10 publications

References 73 publications

Assembly Studies of Two Planar Dy₄ Single-Molecule Magnets

Assembly Studies of Two Planar Dy₄ Single-Molecule Magnets

Synthesis, Structure, and Magnetic Properties of Homometallic Mono-, Penta-, and Hexanuclear Dysprosium Complexes

Chiral Zn₃Ln₃ Hexanuclear Clusters of an Achiral Flexible Ligand

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Slow magnetic relaxation in a Dy3 triangle and a bistriangular Dy6 cluster

Cited by 10 publications

References 73 publications

Assembly Studies of Two Planar Dy4 Single-Molecule Magnets

Assembly Studies of Two Planar Dy4 Single-Molecule Magnets

Synthesis, Structure, and Magnetic Properties of Homometallic Mono-, Penta-, and Hexanuclear Dysprosium Complexes

Chiral Zn3Ln3 Hexanuclear Clusters of an Achiral Flexible Ligand

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Slow magnetic relaxation in a Dy₃ triangle and a bistriangular Dy₆ cluster

Assembly Studies of Two Planar Dy₄ Single-Molecule Magnets

Assembly Studies of Two Planar Dy₄ Single-Molecule Magnets

Chiral Zn₃Ln₃ Hexanuclear Clusters of an Achiral Flexible Ligand