The Interactions Between the Well-Isolated Dy3+ Ions Considerably Contribute to the Demagnetization of Mononuclear Acetylacetonate-Pyrazinate Complex

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-05-09 DOI:10.1039/d5dt00749f

Andrey Vyacheslavovich Gavrikov, Andrey Ilyukhin, Mikhail E. Buzoverov, Konstantin Andreevich Babeshkin, Elena N. Timokhina, Natalia N. Breslavskaya, Pavel Nikolaevich Vasilyev, N. N. Efimov

{"title":"The Interactions Between the Well-Isolated Dy3+ Ions Considerably Contribute to the Demagnetization of Mononuclear Acetylacetonate-Pyrazinate Complex","authors":"Andrey Vyacheslavovich Gavrikov, Andrey Ilyukhin, Mikhail E. Buzoverov, Konstantin Andreevich Babeshkin, Elena N. Timokhina, Natalia N. Breslavskaya, Pavel Nikolaevich Vasilyev, N. N. Efimov","doi":"10.1039/d5dt00749f","DOIUrl":null,"url":null,"abstract":"A series of new mononuclear square antiprismatic complexes comprising acetylacetonate (acac-), pyrazine-2-carboxylate (PyrCOO-) and 1,10-phenanthroline (phen) ligands namely [Ln(acac)2(PyrCOO)(phen)] (Ln is Dy-Yb, Y; 1-5, 6) were prepared and studied. These complexes are new examples of extremely scarcely studied eight-coordinated tetra-chelate complexes comprising β-diketonate and carboxylate ligands. Complexes 1, 3 and 5 exhibit pronounced slowdown of the demagnetization with corresponding pathways additionally validated by the ab initio calculations. In particular, complex 1 exhibits zero-field relaxation with Δeff/kB of 149 K, while the application of the optimal DC field (1500 Oe) enhances Δeff/kB value to 265 K. Thus, although the quantum tunneling of magnetization (QTM) contributes to zero-field relaxation of complex 1, it is among the most efficient zero-field Dy-based SMMs formed by β-diketonate and/or carboxylate ligands. Moreover, Δeff/kB value under the optimal field is the highest one among the related complexes. Interestingly, the Dy-Dy magnetic interactions have considerable effect on the SMM performance of 1 even given the spatial (>8 Å) separation of Dy3+ ions isolated by coats of bulky diamagnetic ligands.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":3.5000,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5dt00749f","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

A series of new mononuclear square antiprismatic complexes comprising acetylacetonate (acac-), pyrazine-2-carboxylate (PyrCOO-) and 1,10-phenanthroline (phen) ligands namely [Ln(acac)2(PyrCOO)(phen)] (Ln is Dy-Yb, Y; 1-5, 6) were prepared and studied. These complexes are new examples of extremely scarcely studied eight-coordinated tetra-chelate complexes comprising β-diketonate and carboxylate ligands. Complexes 1, 3 and 5 exhibit pronounced slowdown of the demagnetization with corresponding pathways additionally validated by the ab initio calculations. In particular, complex 1 exhibits zero-field relaxation with Δeff/kB of 149 K, while the application of the optimal DC field (1500 Oe) enhances Δeff/kB value to 265 K. Thus, although the quantum tunneling of magnetization (QTM) contributes to zero-field relaxation of complex 1, it is among the most efficient zero-field Dy-based SMMs formed by β-diketonate and/or carboxylate ligands. Moreover, Δeff/kB value under the optimal field is the highest one among the related complexes. Interestingly, the Dy-Dy magnetic interactions have considerable effect on the SMM performance of 1 even given the spatial (>8 Å) separation of Dy3+ ions isolated by coats of bulky diamagnetic ligands.

查看原文本刊更多论文

分离良好的Dy3+离子之间的相互作用在很大程度上促进了单核乙酰丙酮-吡嗪酸配合物的退磁

一系列由乙酰丙酮酸（acac-）、吡嗪-2-羧酸酯（PyrCOO-）和1,10-菲罗啉（phen）配体组成的新型单核方形反柱状配合物，即[Ln(acac)2(PyrCOO)(phen)] (Ln为Dy-Yb， Y；1- 5,6)的制备和研究。这些配合物是极少研究的由β-二酮酸盐和羧酸盐配体组成的八配位四螯合配合物的新例子。配合物1、3和5表现出明显的退磁减缓，并通过从头计算验证了相应的路径。特别是配合物1表现出零场弛豫，Δeff/kB为149 K，而最优直流场（1500 Oe）的应用使Δeff/kB值提高到265 K。因此，虽然量子隧穿磁化（QTM）有助于配合物1的零场弛豫，但它是由β-二酮酸盐和/或羧酸盐配体形成的最有效的零场镝基smm之一。最优场下的Δeff/kB值是相关配合物中最高的。有趣的是，Dy-Dy磁相互作用对1的SMM性能有相当大的影响，即使考虑到空间（>8 Å）分离的Dy3+离子被大块的抗磁性配体涂层隔离。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

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.