Trinuclear ZnII-LnIII Complexes: Single-Ion Magnet Behavior in the Zn2Dy Analogue

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2025-03-25 DOI:10.1021/acs.cgd.5c0011410.1021/acs.cgd.5c00114

Soumalya Roy, Botan Li, Ezhava Manu Manohar, Arup Sarkar*, Sukanta Saha, Lin Sun*, Atanu Dey*, Junseong Lee* and Sourav Das*,

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Abstract

Placing diamagnetic transition metal ions in the vicinity of lanthanide ions separated by a single coordinated oxygen atom has emerged as an effective strategy to suppress quantum tunneling of magnetization (QTM), thereby enhancing the performance of single-molecule magnets. In this context, we have synthesized trinuclear Zn^II-Ln^III [LnZn₂L₂(CH₃COO)₂(H₂O)(CH₃OH)]·NO₃ (Ln= Dy(1) and Gd(2)) complexes employing a multisite coordinating Schiff base ligand, (E)-2-(hydroxymethyl)-4-methyl-6-[{(pyridine-2-ylmethyl)imino}methyl]phenol, in the presence of Ln(NO₃)₃.xH₂O and Zn(OAc)₂·2H₂O. The complexes crystallize in the monoclinic crystal system with the P2₁/c space group. The trimetallic system mainly consists of two Zn ions, one Ln ion, two deprotonated ligands, a solvent molecule (CH₃OH), aqua ligands, and NO₃^– present outside the coordination sphere. Magnetic studies demonstrate complex 1 as a single ion magnet with U_eff = 56.88 K and pre-exponential parameter τ = 1.94 × 10^–6 s. State-average CASSCF/RASSI-SO calculations performed on the Zn₂Dy complex reveal a large magnetization reversal barrier of 375 cm^–1 which is in accordance with the field-induced SMM behavior of this complex.

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三核ni - lniii配合物：Zn2Dy类似物中的单离子磁铁行为

在由单个配位氧原子分离的镧系离子附近放置抗磁性过渡金属离子是抑制量子隧穿磁化（QTM）的有效策略，从而提高了单分子磁体的性能。在这种情况下，我们在Ln(NO3)3的存在下，利用多位点配位席夫碱配体(E)-2-（羟甲基）-4-甲基-6-[{（吡啶-2-甲基）亚氨基}甲基]苯酚合成了三核的ZnII-LnIII [LnZn2L2(CH3COO)2(H2O)(CH3OH)]·NO3 (Ln= Dy（1)和Gd(2)）配合物。xH2O和Zn(OAc)2·2H2O。配合物在单斜晶系中结晶，具有P21/c空间基团。三金属体系主要由两个Zn离子、一个Ln离子、两个去质子化配体、一个溶剂分子（CH3OH）、水合配体和存在于配位球外的NO3 -组成。磁性研究表明，配合物1为单离子磁铁，Ueff = 56.88 K，指前参数τ = 1.94 × 10-6 s。对Zn2Dy配合物进行的状态平均CASSCF/ rasi - so计算显示，该配合物具有375 cm-1的大磁化反转势垒，这与该配合物的场致SMM行为一致。

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.