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
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
{"title":"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","authors":"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","doi":"10.1039/d4dt01779j","DOIUrl":null,"url":null,"abstract":"The reactions of VOSO<small><sub>4</sub></small>·3H<small><sub>2</sub></small>O with Na<small><sub>2</sub></small>(cbdc) (cbdc<small><sup>2−</sup></small> – dianion of cyclobutane-1,1-dicarboxylic acid) and lanthanide(<small>III</small>) nitrates taken in a molar ratio of 1 : 2 : 1 were found to yield a series of isostructural heterometallic compounds [NaLn(VO)<small><sub>2</sub></small>(cbdc)<small><sub>4</sub></small>(H<small><sub>2</sub></small>O)<small><sub>10</sub></small>]<small><sub><em>n</em></sub></small> (<strong>1<small><sub>Ln</sub></small></strong>, Ln = Tb, Dy, Ho, Er, Tm, Yb). These compounds are constructed from trinuclear anionic units [Ln(VO)<small><sub>2</sub></small>(cbdc)<small><sub>4</sub></small>(H<small><sub>2</sub></small>O)<small><sub>8</sub></small>]<small><sup>−</sup></small> ({LnV<small><sub>2</sub></small>}<small><sup>−</sup></small>) linked by Na<small><sup>+</sup></small> ions into 1D polymeric chains. The crystal structures of <strong>1<small><sub>Dy</sub></small></strong> and <strong>1<small><sub>Er</sub></small></strong> were determined by single-crystal X-ray diffraction (XRD), and their isostructurality with <strong>1<small><sub>Tb</sub></small></strong>, <strong>1<small><sub>Ho</sub></small></strong>, <strong>1<small><sub>Tm</sub></small></strong>, and <strong>1<small><sub>Yb</sub></small></strong> was proved by powder X-ray diffraction (PXRD). According to alternating current (ac) magnetic susceptibility measurements, <strong>1<small><sub>Dy</sub></small></strong>, <strong>1<small><sub>Er</sub></small></strong>, and <strong>1<small><sub>Yb</sub></small></strong> exhibited field-induced slow relaxation of magnetization. Compound <strong>1<small><sub>Er</sub></small></strong> is the first representative of Er<small><sup>III</sup></small>–V<small><sup>IV</sup></small> single-molecule magnets. Measuring the temperature dependences of the phase memory time (<em>T</em><small><sub>m</sub></small>) for <strong>1<small><sub>Dy</sub></small></strong> and <strong>1<small><sub>Yb</sub></small></strong> 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.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-10-24","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/d4dt01779j","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 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 (1Ln, 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 1Dy and 1Er were determined by single-crystal X-ray diffraction (XRD), and their isostructurality with 1Tb, 1Ho, 1Tm, and 1Yb was proved by powder X-ray diffraction (PXRD). According to alternating current (ac) magnetic susceptibility measurements, 1Dy, 1Er, and 1Yb exhibited field-induced slow relaxation of magnetization. Compound 1Er is the first representative of ErIII–VIV single-molecule magnets. Measuring the temperature dependences of the phase memory time (Tm) for 1Dy and 1Yb 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.
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.