Investigation of slow magnetic relaxation in a series of 1D polymeric cyclobutane-1,1-dicarboxylates based on LnIIIVIV2 units (LnIII = Tb, Dy, Ho, Er, Tm, Yb): rare examples of VIV-4f single-molecule magnets

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2024-10-24 DOI:10.1039/d4dt01779j

Evgeniya S. Bazhina, Maxim A. Shmelev, Natalia V. Gogoleva, Konstantin A. Babeshkin, Ivan V. Kurganskii, Nikolay N. Efimov, Matvey V. Fedin, Mikhail A. Kiskin, Igor L. Eremenko

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Abstract

The reactions of VOSO₄·3H₂O with Na₂(cbdc) (cbdc²⁻ – dianion of cyclobutane-1,1-dicarboxylic acid) and lanthanide(III) nitrates taken in a molar ratio of 1 : 2 : 1 were found to yield a series of isostructural heterometallic compounds [NaLn(VO)₂(cbdc)₄(H₂O)₁₀]_n (1_Ln, Ln = Tb, Dy, Ho, Er, Tm, Yb). These compounds are constructed from trinuclear anionic units [Ln(VO)₂(cbdc)₄(H₂O)₈]⁻ ({LnV₂}⁻) linked by Na⁺ ions into 1D polymeric chains. The crystal structures of 1_Dy and 1_Er were determined by single-crystal X-ray diffraction (XRD), and their isostructurality with 1_Tb, 1_Ho, 1_Tm, and 1_Yb was proved by powder X-ray diffraction (PXRD). According to alternating current (ac) magnetic susceptibility measurements, 1_Dy, 1_Er, and 1_Yb exhibited field-induced slow relaxation of magnetization. Compound 1_Er is the first representative of Er^III–V^IV single-molecule magnets. Measuring the temperature dependences of the phase memory time (T_m) for 1_Dy and 1_Yb using pulsed EPR spectroscopy allowed us to observe the phenomenon of phase relaxation enhancement (PRE) at temperatures below 30 K. In future, this phenomenon may contribute to the evaluation of relaxation times of the lanthanide ions.

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VOSO4-3H2O 与 Na2(cbdc)（cbdc2--环丁烷-1,1-二羧酸的二元离子）和硝酸镧（III）以 1 : 2 ：1 的摩尔比生成一系列等结构异金属化合物 [NaLn(VO)2(cbdc)4(H2O)10]n（1Ln，Ln = Tb、Dy、Ho、Er、Tm、Yb）。这些化合物是由三核阴离子单元[Ln(VO)2(cbdc)4(H2O)8]-（{LnV2}-）通过 Na+离子连接成一维聚合物链而成。单晶 X 射线衍射 (XRD) 确定了 1Dy 和 1Er 的晶体结构，粉末 X 射线衍射 (PXRD) 证明了它们与 1Tb、1Ho、1Tm 和 1Yb 的同构性。根据交流电（ac）磁感应强度测量，1Dy、1Er 和 1Yb 表现出场诱导的缓慢磁化弛豫。化合物 1Er 是 ErIII-VIV 单分子磁体的首个代表。利用脉冲 EPR 光谱法测量 1Dy 和 1Yb 的相记忆时间 (Tm) 的温度相关性，使我们能够观察到温度低于 30 K 时的相弛豫增强 (PRE) 现象。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.