Synergistic structural-electronic strategy enhances magnetic relaxation in DyIII single-molecule magnets

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2025-06-11 DOI:10.1016/j.molstruc.2025.142974

Lin-Bo Cao, Han Yan, Qi Tan, Wen-Bin Sun

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引用次数: 0

Abstract

Three new binuclear dysprosium complexes bridged by 4‑hydroxy-3,5-dimethoxybenzaldehyde (DMOAP), 2,6-dimethoxyphenol (DMOP), and 2,6-dimethoxy-4-methylphenol (DMOMP), formulated as [Dy₂(NO₃)₄(DMOAP)₂(SCN)₂]·2(Et)₃NH (1), [Dy₂(NO₃)₄(DMOP)₂(SCN)₂]·2(Et)₃NH (2) and [Dy₂(NO₃)₄(DMOMP)₂(SCN)₂]·2(Et)₃NH (3) were structurally and magnetically characterized. By varying the substituents on the DMOP bridge (electron-withdrawing and donating groups), we achieved fine-tuning of the Dy-Dy distances and the modulation to the Dy-Dy magnetic interactions, which ultimately resulting in enhanced single-molecule magnetic (SMM) properties. Dynamic magnetic measurement revealed that complexes 1–3 all exhibit characteristic single-molecule magnet behavior with effective energy barriers of 54.62 K, 105.46 K, and 129.96 K, respectively. Notably, complex 3 bridged by methyl-substituted DMOP exhibits magnetic hysteresis up to 4 K and a clear open hysteresis loop with a coercive field of 221 Oe is observed under zero applied DC field at 1.9 K, which is rarely observed in non-radical-bridged binuclear lanthanide SMMs.

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协同结构-电子策略增强DyIII单分子磁体的磁弛豫

以4-羟基-3,5-二甲氧基苯甲醛（DMOAP）、2,6-二甲氧基苯酚（DMOP）和2,6-二甲氧基-4-甲基苯酚（DMOMP）为桥接物，合成了[Dy2(NO3)4(DMOAP)2(SCN)2]·2(Et)3NH(1)、[Dy2(NO3)4(DMOP)2(SCN)2]·2（Et)3NH(2)）和[Dy2(NO3)4(DMOMP)2(SCN)2]·2（Et)3NH(3)）三种新型双核镝配合物。通过改变DMOP桥上的取代基（吸电子基和供电子基），我们实现了Dy-Dy距离的微调和Dy-Dy磁相互作用的调制，最终导致单分子磁性（SMM）性能的增强。动态磁性测量表明，配合物1-3均表现出典型的单分子磁性行为，有效能垒分别为54.62 K、105.46 K和129.96 K。值得注意的是，甲基取代DMOP桥接的配合物3表现出高达4 K的磁滞，并且在1.9 K的零直流场下观察到一个清晰的开放磁滞环，其顽固性场为221 Oe，这在非自由基桥接的双核镧系smm中很少观察到。

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

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