Lanthanide-Based Single-Molecule Magnets Derived from Lacunary Polyoxometalates

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2025-03-13 DOI:10.1021/acs.cgd.5c0011110.1021/acs.cgd.5c00111

Kenta Hirakawa, Yoshihiro Sekine, Fumiya Kobayashi, Yoji Horii, Hikaru Zenno, Manabu Nakaya and Shinya Hayami*,

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引用次数: 0

Abstract

Toward the development of new functional materials with single-molecule magnet (SMM) behavior, novel lacunary Dawson-type polyoxometalate (POM)-based clusters containing lanthanide ions (Dy³⁺ and Tb³⁺) were synthesized and their applicability as SMMs was verified. Four discrete complexes were obtained at a mixing ratio of lanthanide ions to lacunary POM clusters of 2:2 or 1:2, yielding K₁₄[Dy₂(P₂W₁₇O₆₁)₂]·52H₂O (1), K₁₇[Dy(P₂W₁₇O₆₁)₂]·52H₂O (2), K₁₄[Tb₂(P₂W₁₇O₆₁)₂]·52H₂O (3), and K₁₇[Tb(P₂W₁₇O₆₁)₂]·53H₂O (4), which were characterized by single-crystal X-ray structural analysis. Detailed measurements of the alternating current (ac) magnetic properties revealed that 1 and 2 exhibited the SMM behavior (U_eff/k_B = 2.19 and 22.23 K, τ₀ = 9.02 × 10^–7 and 4.56 × 10^–5 s, H_dc = 3000 and 1000 Oe, respectively), unlike 3 and 4. The distorted geometry of Dy³⁺ ions in 2 in relation to that in 1 resulted in slow magnetic relaxation caused by SMMs with larger energy barrier values, according to temperature-dependent ac susceptibility measurements and theoretical calculations. Therefore, new hybrid materials as SMMs from trivalent lanthanide ions and lacunary POM clusters can be fabricated. This study opens new avenues for constructing next-generation compounds that exhibit interesting slow magnetic relaxation based on the assembly of lanthanide ions and lacunary POMs.

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.