Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Ditert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2024-12-21 DOI:10.1021/acs.inorgchem.4c03278

Svetlana V. Klementyeva, Michael T. Gamer, Michael Schulze, Nithin Suryadevara, Artem S. Bogomyakov, Pavel A. Abramov, Sergey N. Konchenko, Mario Ruben, Wolfgang Wernsdorfer, Eufemio Moreno-Pineda

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Abstract

The dinuclear β-diketiminato complex [L¹ClDy(μ-Cl)₃DyL¹(THF)] (1) (L¹ = {2,6-ⁱPr₂C₆H₃–NC(Me)CHC(Me)N-2,6-ⁱPr₂C₆H₃}⁻) was obtained by reaction of DyCl₃ with KL¹ in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [L¹Dy(μ-3,5-Cat)]₂ (2) by salt metathesis reaction with 3,5-CatK₂ (3,5-Cat −3,5-di-tert-butyl-catecholate). Reactions of 3,5-CatNa₂ with [L²LnCl₂(THF)₂] (Ln³⁺ = Dy, Y) ligated with the less bulky ligand L² = {2,4,6-Me₃C₆H₂–NC(Me)CHC(Me)N-2,4,6-Me₃C₆H₂}⁻ afforded the mixed-ligand THF-containing complexes [L²Ln(μ-3,5-Cat)(THF)]₂ (Ln³⁺ = Dy (3a), Y (3b)). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction. Magnetic measurements revealed single-molecule magnet behavior for the dysprosium complexes. Sub-Kelvin μSQUID studies confirm the SMM character of the systems, while CASSCF calculation along with simulation of the experimental data yields an antiferromagnetic interaction operating between the Dy³⁺ ions.

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具有桥接3,5-二叔丁基儿茶酚酸酯的双核稀土β-二酮酸盐：合成、结构和单分子磁性

由DyCl3与KL1以1:1的摩尔比反应得到双核β-二酮酸配合物[L1ClDy(μ-Cl)3DyL1(THF)] (1) (L1 = {2,6- ipr2c6h3 - nc (Me)CHC(Me) n -2,6- ipr2c6h3}−)，并与3,5- catk2 （3,5- cat−3,5-二叔丁基儿茶酚酸盐）进行盐还原反应制备混合配体配合物[L1Dy(μ-3,5- cat)]2(2)。与体积较小的配体L2 = {2,4,6- me3c6h2 - nc (Me)CHC(Me) n -2,4,6- me3c6h2}−结合的3,5- catna2与[L2Ln(μ-3,5- cat)(THF)]2 (Ln3+ = Dy （3a), Y (3b)）反应得到混合配体含THF配合物[L2Ln(μ-3,5- cat)]2 (Ln3+ = Dy （3a), Y (3b)）。所有新的配合物都被充分表征，并通过单晶x射线衍射确定了固体结构。磁性测量揭示了镝配合物的单分子磁性行为。亚开尔文μSQUID研究证实了系统的SMM特性，而CASSCF计算和实验数据的模拟得到了Dy3+离子之间的反铁磁相互作用。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.