Solvent-dependent Ln(iii) clusters assembled by immobilization of CO2 in air: zero-field single-molecule magnets and magnetic refrigerant materials†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Cai-Ming Liu, Xiang Hao, Zhao-Bo Hu and He-Rui Wen
{"title":"Solvent-dependent Ln(iii) clusters assembled by immobilization of CO2 in air: zero-field single-molecule magnets and magnetic refrigerant materials†","authors":"Cai-Ming Liu, Xiang Hao, Zhao-Bo Hu and He-Rui Wen","doi":"10.1039/D4DT02310B","DOIUrl":null,"url":null,"abstract":"<p >The automatic fixation of CO<small><sub>2</sub></small> in air played a key role in the construction of Dy(<small>III</small>) single-molecule magnets (SMMs) and Gd(<small>III</small>) magnetic refrigeration molecular materials when Ln(<small>III</small>)Cl<small><sub>3</sub></small> (Ln = Dy and Gd) was reacted with a new hydrazone Schiff base ligand {H<small><sub>2</sub></small>L = (<em>E</em>)-<em>N</em>′-(4-fluoro-2-hydroxybenzylidene)pyrimidine-4-carbohydrazide}, which is condensed from pyrimidine-4-carbohydrazide and 4-fluorosalicylaldehyde. Surprisingly, the small difference in methanol and ethanol solvents leads to dramatic changes in the structures of these Ln(<small>III</small>) cluster complexes. When methanol and ethanol participated in the reaction, a trapezoidal pyramid Dy(<small>III</small>) pentanuclear cluster [Dy<small><sub>5</sub></small>L<small><sub>5</sub></small>(OH)<small><sub>2</sub></small>(CO<small><sub>3</sub></small>)(O<small><sub>2</sub></small>COMe)(MeOH)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)]·3MeOH·3.5H<small><sub>2</sub></small>O (<strong>1</strong>) and a triangular prism Dy(<small>III</small>) hexanuclear cluster [Dy<small><sub>6</sub></small>L<small><sub>6</sub></small>(CO<small><sub>3</sub></small>)<small><sub>2</sub></small>(EtOH)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>Cl<small><sub>2</sub></small>]·6EtOH (<strong>2</strong>) were obtained, respectively, and a tub-like Gd(<small>III</small>) octanuclear cluster [Gd<small><sub>8</sub></small>L<small><sub>8</sub></small>(CO<small><sub>3</sub></small>)<small><sub>4</sub></small>(MeOH)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>]·12MeOH·3CH<small><sub>2</sub></small>Cl<small><sub>2</sub></small>·3.25H<small><sub>2</sub></small>O (<strong>3</strong>) and a trapezoidal pyramid Gd(<small>III</small>) pentanuclear cluster [Gd<small><sub>5</sub></small>L<small><sub>4</sub></small>(HL)(CO<small><sub>3</sub></small>)O(OH)(EtOH)<small><sub>5</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>Cl]·EtOH·3H<small><sub>2</sub></small>O (<strong>4</strong>) were yielded, respectively. Notably, <strong>1</strong> contains not only the carbonate anion, but also the monomethyl carbonate anion as the bridging ligand, which are formed by immobilizing CO<small><sub>2</sub></small> in air, while <strong>2</strong>, <strong>3</strong> and <strong>4</strong> contain the carbonate bridging ligand only. Magnetic properties’ investigations revealed that both <strong>1</strong> and <strong>2</strong> are zero-field SMMs, with <em>U</em><small><sub>eff</sub></small>/<em>k</em> values of 93.2 K and 133.5 K, respectively, while <strong>3</strong> and <strong>4</strong> show large magnetocaloric effects, with the largest −Δ<em>S</em><small><sub>m</sub></small> values of 27.49 J kg<small><sup>−1</sup></small> K<small><sup>−1</sup></small> at 2.0 K for Δ<em>H</em> = 7 T for <strong>3</strong> and 27.58 J kg<small><sup>−1</sup></small> K<small><sup>−1</sup></small> at 2.5 K for Δ<em>H</em> = 7 T for <strong>4</strong>.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 1","pages":" 96-107"},"PeriodicalIF":3.5000,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt02310b","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

The automatic fixation of CO2 in air played a key role in the construction of Dy(III) single-molecule magnets (SMMs) and Gd(III) magnetic refrigeration molecular materials when Ln(III)Cl3 (Ln = Dy and Gd) was reacted with a new hydrazone Schiff base ligand {H2L = (E)-N′-(4-fluoro-2-hydroxybenzylidene)pyrimidine-4-carbohydrazide}, which is condensed from pyrimidine-4-carbohydrazide and 4-fluorosalicylaldehyde. Surprisingly, the small difference in methanol and ethanol solvents leads to dramatic changes in the structures of these Ln(III) cluster complexes. When methanol and ethanol participated in the reaction, a trapezoidal pyramid Dy(III) pentanuclear cluster [Dy5L5(OH)2(CO3)(O2COMe)(MeOH)3(H2O)]·3MeOH·3.5H2O (1) and a triangular prism Dy(III) hexanuclear cluster [Dy6L6(CO3)2(EtOH)2(H2O)2Cl2]·6EtOH (2) were obtained, respectively, and a tub-like Gd(III) octanuclear cluster [Gd8L8(CO3)4(MeOH)3(H2O)5]·12MeOH·3CH2Cl2·3.25H2O (3) and a trapezoidal pyramid Gd(III) pentanuclear cluster [Gd5L4(HL)(CO3)O(OH)(EtOH)5(H2O)2Cl]·EtOH·3H2O (4) were yielded, respectively. Notably, 1 contains not only the carbonate anion, but also the monomethyl carbonate anion as the bridging ligand, which are formed by immobilizing CO2 in air, while 2, 3 and 4 contain the carbonate bridging ligand only. Magnetic properties’ investigations revealed that both 1 and 2 are zero-field SMMs, with Ueff/k values of 93.2 K and 133.5 K, respectively, while 3 and 4 show large magnetocaloric effects, with the largest −ΔSm values of 27.49 J kg−1 K−1 at 2.0 K for ΔH = 7 T for 3 and 27.58 J kg−1 K−1 at 2.5 K for ΔH = 7 T for 4.

Abstract Image

通过固定空气中的二氧化碳而组装的溶剂依赖性锰(III)团簇:零场单分子磁体和磁性制冷材料
在利用 Ln(III)Cl3 (Ln = Dy 和 Gd)和一种新的腙席夫碱配体 {H2L = (E)-N'-(4-fluoro-2-hydroxybenzylidene)pyrimidine-4-carbohydrazide} 构建 Dy(III) 单分子磁体 (SMM) 和 Gd(III) 磁性制冷分子材料的过程中,空气中 CO2 的自动固定起着关键作用、由嘧啶-4-甲酰肼和 4-氟水杨醛缩合而成。令人惊讶的是,甲醇和乙醇溶剂的细微差别导致镧(III)簇络合物的结构发生了巨大变化。当甲醇和乙醇参与反应时,梯形金字塔的 Dy(III)五核簇[Dy5L5(OH)2(CO3)(O2COMe)(MeOH)3(H2O)]⸱3MeOH-3.5H2O(1)和三角棱柱 Dy(III)六核团簇[Dy6L6(CO3)2(EtOH)2(H2O)2(Cl)2]⸱6EtOH;以及管状 Gd(III)八核团簇[Gd8L8(CO3)4(MeOH)3(H2O)5]⸱12MeOH-3CH2Cl2-3.25H2O(3)和梯形金字塔五核钆(III)簇[Gd5L4(HL)(CO3)(O)(OH)(EtOH)5(H2O)2(Cl)]⸱EtOH⸱3H2O(4)。值得注意的是,络合物 1 不仅含有碳酸阴离子,还含有碳酸单甲酯阴离子作为桥接配体,它们是通过固定空气中的 CO2 而形成的,而络合物 2、3 和 4 只含有碳酸桥接配体。磁性研究表明,1 和 2 均为零磁场 SMM,Ueff/k 值分别为 93.2 K 和 133.5 K;而 3 和 4 则显示出较大的磁致效应,其中 3 的 -ΔSm 值最大,在 2.0 K 时为 27.52 Jkg-1K-1(ΔH = 7 T),而 4 的 -ΔSm 值最大,在 2.5 K 时为 27.58 Jkg-1K-1(ΔH = 7 T)。
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
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.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信