Topology-Enforced Tetranuclear [M2Dy2] Stair-like Assembly: Interplay between Single-Ion Anisotropy and Long-Distance Dipolar Effects

IF 3.6 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2026-10-07 Epub Date: 2026-09-08 DOI:10.1021/acs.cgd.6c00573

Li-Hsin Chang, Cheng-Lun Tsai, Jérôme Long, Po-Heng Lin

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Abstract

We report the synthesis, crystal structures, and magnetic properties of three tetranuclear [M₂Dy₂] complexes, [Dy₂Ni₂(Hhmb)₂(hmb)₂(NO₃)₂(IMA)₂] (1), [Dy₂Cu₂(Hhmb)₂(hmb)₂(NO₃)₂(IMA)₂]·Acetone (2), and [Dy₂Cu₂(Hhmb)₂(hmb)₂(H₂O)₄(IMA)₂](CF₃SO₃)₂·4THF·2Acetone (3) (H₂hmb = 2-hydroxy-3-methoxyphenyl)methylene(benzonicotino)hydrazine; HIMA = Imidazole-1-ylacetic acid). These complexes feature a rare stair-like topology enforced by a rigid dual-protonation ligand framework. This step-like arrangement maintains a central {Dy₂} core while positioning the 3d metal ions at relatively large distances, providing a platform to probe the influence of remote paramagnetic centers on relaxation dynamics. Magnetic measurements reveal field-induced slow relaxation of the magnetization for complexes 1 and 2, with markedly slower relaxation in the Ni²⁺ analogues compared to the isomorphous Cu²⁺ derivative, highlighting a detrimental effect of the paramagnetic Cu²⁺ centers despite their remote position. Ab initio calculations reveal that while 1 and 2 share nearly identical single-ion anisotropy profiles, the remote Cu²⁺ centers introduce weak dipolar fields that might accelerate the quantum tunneling. For complex 3, the introduction of coordinated water molecules directly alters the coordination sphere, weakening the local axial crystal field and further exacerbating these disruptive effects. This work underscores the need to jointly consider single-ion axiality and long-range dipolar coupling when designing heterometallic single-molecule magnets.

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拓扑强制四核[M2Dy2]阶梯组装：单离子各向异性和远距离偶极效应之间的相互作用

本文报道了三种四核[M2Dy2]配合物[Dy2Ni2(Hhmb)2(hmb)2(NO3)2(IMA)2](1)、[Dy2Cu2(Hhmb)2(hmb)2(NO3)2(IMA)2]·丙酮(2)和[Dy2Cu2(Hhmb)2(hmb)2(H2O)4(IMA)2](CF3SO3)2·4THF·2Acetone (3)) （H2hmb = 2-羟基-3-甲氧基苯基）亚甲基（苯并烟碱）肼的合成、晶体结构和磁性能；咪唑-1-基乙酸)。这些配合物具有罕见的阶梯状拓扑结构，由刚性双质子化配体框架强制执行。这种阶梯状排列保持了中心{Dy2}核，同时将三维金属离子定位在相对较远的距离上，为探测远程顺磁中心对弛豫动力学的影响提供了一个平台。磁场测量显示，配合物1和2的磁场诱导的磁化弛豫缓慢，与同构Cu2+衍生物相比，Ni2+类似物的弛豫明显较慢，突出了顺磁性Cu2+中心的不利影响，尽管它们的位置遥远。从头计算表明，虽然1和2具有几乎相同的单离子各向异性，但远Cu2+中心引入了弱偶极场，可能会加速量子隧穿。对于配合物3，配位水分子的引入直接改变了配位球，削弱了局部轴向晶体场，进一步加剧了这些破坏作用。这项工作强调了在设计异质金属单分子磁体时需要联合考虑单离子轴向性和远程偶极耦合。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.