Solvent-Induced Magnetic Properties of a Series of Dy-Based MOFs from Two Different Precursor Complexes

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-11-04 DOI:10.1021/acs.cgd.4c0119010.1021/acs.cgd.4c01190

Wen-Kang Jiang, Ting-Ting Huang, Dong-Xiu Lv, Zhong-Hong Zhu*, Hua-Hong Zou* and Fu-Pei Liang*,

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Abstract

It is still challenging for Dy-MOFs to modulate the single-molecule magnet (SMM) behavior through guest molecules. Dy-MOFs with different guest molecules, secondary building units, and linkers were synthesized by precursors and bridging carboxylic acid ligands, and the magnetic properties of Dy-MOFs were regulated by guest molecules. These differentiated Dy-MOFs are [Dy₂(C₉H₄Cl₂NO)₂(L1)₂(H₂O)(DMA)]_n·DMA (MOF-3, L1 = terephthalate), [Dy(C₉H₄Cl₂NO)₂(L1)(DMSO)(H₂O)]_n (MOF-4), [Dy₂(C₉H₄Br₂NO)₂(L1)₂(H₂O)(DMA)]_n·DMA (MOF-5), [Dy(C₉H₄Cl₂NO)₂(L2)(H₂O)]_n·DMA (MOF-6, L2 = isophthalate), and [Dy(C₉H₄Cl₂NO)₂(L2)(H₂O)]_n·DMF (MOF-7), [Dy(C₉H₄Br₂NO)₂(L2)(H₂O)]_n·DMA (MOF-8). The single-crystal X-ray diffraction showed that MOF-3 and MOF-5 are two-dimensional MOFs with square holes. MOF-4 is a two-dimensional MOF formed by hydrogen–halogen bonds, and MOF-6, MOF-7, and MOF-8 are one-dimensional chains. The magnetic test results show that MOF-4, MOF-6, and MOF-8 show SMM behavior under zero field, and MOF-3 and MOF-5 exhibit field-induced SMM behavior. In the zero field, the effective energy bases of MOF-4, MOF-6, and MOF-8 are 37.09, 19.56, and 15.73 K, and relaxation times τ₀ were 4.66 × 10^–6, 2.35 × 10^–6, and 9.95 × 10^–6 s, respectively. This work provides a vivid example of regulating the molecular magnetism of Dy-MOFs and promotes the progress of Dy-MOF crystal engineering.

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两种不同前驱体复合物的镝基 MOFs 系列的溶剂诱导磁性能

通过客体分子调控单分子磁体（SMM）行为对 Dy-MOFs 来说仍然具有挑战性。研究人员通过前体和桥接羧酸配体合成了具有不同客体分子、二级结构单元和连接体的 Dy-MOF，并通过客体分子调控 Dy-MOF 的磁性。这些差异化的 Dy-MOFs 包括[Dy2(C9H4Cl2NO)2(L1)2(H2O)(DMA)]n-DMA（MOF-3，L1 = 对苯二甲酸盐）、[Dy(C9H4Cl2NO)2(L1)(DMSO)(H2O)]n（MOF-4）、[Dy2(C9H4Br2NO)2(L1)2(H2O)(DMA)]n-DMA（MOF-5）、[Dy(C9H4Cl2NO)2(L2)(H2O)]n-DMA（MOF-6，L2 = 间苯二甲酸盐），以及[Dy(C9H4Cl2NO)2(L2)(H2O)]n-DMF（MOF-7）、[Dy(C9H4Br2NO)2(L2)(H2O)]n-DMA（MOF-8）。单晶 X 射线衍射显示，MOF-3 和 MOF-5 是具有方孔的二维 MOF。MOF-4 是由氢卤键形成的二维 MOF，MOF-6、MOF-7 和 MOF-8 是一维链。磁场测试结果表明，MOF-4、MOF-6 和 MOF-8 在零磁场下表现出 SMM 行为，而 MOF-3 和 MOF-5 则表现出磁场诱导的 SMM 行为。在零场中，MOF-4、MOF-6 和 MOF-8 的有效能基分别为 37.09、19.56 和 15.73 K，弛豫时间 τ0 分别为 4.66 × 10-6、2.35 × 10-6 和 9.95 × 10-6 s。这项工作为调节 Dy-MOF 的分子磁性提供了一个生动的实例，推动了 Dy-MOF 晶体工程学的发展。

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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.