Supermolecular Aggregates of Mononuclear and Asymmetric Dinuclear Dysprosium Single-Molecule Magnets Assembled by Intermolecular Hydrogen Bonds

IF 3.4 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-07-18 DOI:10.1021/acs.cgd.4c0024610.1021/acs.cgd.4c00246

Yu Qin, Cui-E Wu, Chun-Jiang Li, Zhan-Ting Cai, Bei Hu, Quan-Bo Wang, Zilu Chen*, Fu-Pei Liang* and Kai Wang*,

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Abstract

By manipulating the aggregate states of dysprosium single-molecule magnets (Dy^III-SMMs), the hydrogen bonds have played key roles in realizing aggregation-induced suppression of quantum tunneling of magnetization (QTM), thus becoming a new tool to optimize the performance of Dy^III-SMMs. Yet, supermolecular aggregates of Dy^III-SMMs assembled by hydrogen bonds are still scarcely reported so far. Herein, two such aggregates, [Dy(H₃spho)(NO₃)₂(CH₃OH)₂]·CH₃OH (SAH-1) and [Dy₂(H₂cspho)(NO₃)₄(CH₃OH)₃(H₂O)]·2CH₃CN (SAH-2), were prepared by N,N′-bis(salicylicdene)pyridine-2,6-dicarbohydrazide N-oxide (H₄spho) and N,N′-bis(5-chlorosalicylicdene) pyridine-2,6-dicarbohydrazide N-oxide (H₄cspho), respectively. SAH-1 shows a supermolecular dimer structure, where two mononuclear molecules are linked together by hydrogen bonds and arranged in a side-by-side fashion. SAH-2 is a three-dimensional (3D) hydrogen-bonded organic framework (HOF). Its molecule features an asymmetric dinuclear {Dy₂} structure based on a single symmetric ligand, which has not been observed in the whole lanthanide complex family. Both SAH-1 and SAH-2 exhibit desirable SMM behavior, with the highest effective energy barrier (U_eff) of 67(2) and 62(3) K, respectively. SAH-2 also displays field-induced dual-relaxation behavior. The magnetic dilution experiments reveal that the dipole interactions relating to supermolecular aggregate states have non-negligible effects on the relaxation of SAH-1 and SAH-2.

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通过分子间氢键组装的单核和不对称双核镝单分子磁体的超分子聚合体

通过操纵镝单分子磁体（DyIII-SMMs）的聚集态，氢键在实现聚集诱导的磁化量子隧道（QTM）抑制方面发挥了关键作用，从而成为优化 DyIII-SMMs 性能的新工具。然而，迄今为止，通过氢键组装的DyIII-SMMs超分子聚集体仍鲜有报道。N′-双（水杨醛）吡啶-2,6-二甲酸肼 N-氧化物（H4spho）和 N,N′-双（5-氯水杨醛）吡啶-2,6-二甲酸肼 N-氧化物（H4cspho）制备的。SAH-1 呈超分子二聚体结构，两个单核分子通过氢键连接在一起，并排排列。SAH-2 是一种三维氢键有机框架（HOF）。它的分子具有基于单一对称配体的不对称双核{Dy2}结构，这在整个镧系元素复合物家族中都没有发现过。SAH-1 和 SAH-2 都表现出理想的 SMM 行为，其最高有效能垒（Ueff）分别为 67(2) K 和 62(3) K。SAH-2 还表现出场诱导的双松弛行为。磁稀释实验表明，与超分子聚集态有关的偶极相互作用对 SAH-1 和 SAH-2 的弛豫具有不可忽略的影响。

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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.