{"title":"Sandglass-like Ln9 Nanoclusters with Magnetocaloric Effect and Lanthanide-Centered Luminescence","authors":"Tiantian Wang, Hao Wang, Wenbin Sun","doi":"10.1021/acs.cgd.4c01031","DOIUrl":null,"url":null,"abstract":"It is a challenging work to construct high-nuclear lanthanide nanoclusters with desirable magnetocaloric effects. To this end, a series of Ln<sub>9</sub> nanoclusters with sandglass-like topological structures have been successfully synthesized under solvothermal conditions by using two different alcoholamine ligands and lanthanide (Ln<sup>III</sup>) salts, with the molecular formula [Ln<sub>9</sub>(L<sup>1</sup>)<sub>4</sub>(NO<sub>3</sub>)<sub>12</sub>(μ<sub>3</sub>-OH)<sub>8</sub>(μ<sub>4</sub>-OH)<sub>2</sub>(CH<sub>3</sub>CH<sub>2</sub>OH)<sub>4</sub>]·4.5CH<sub>3</sub>CH<sub>2</sub>OH·3Et<sub>3</sub>NH (Ln<sup>III</sup> = Gd (<b>1-Gd</b>), Eu (<b>1-Eu</b>), Tb (<b>1-Tb</b>)) and [Ln<sub>9</sub>(L<sup>2</sup>)<sub>8</sub>(NO<sub>3</sub>)<sub>8</sub>(μ<sub>3</sub>-OH)<sub>8</sub>(μ<sub>4</sub>-OH)<sub>2</sub>]·NO<sub>3</sub> (Ln<sup>III</sup> = Gd (<b>2-Gd</b>), Eu (<b>2-Eu</b>), Tb (<b>2-Tb</b>)) (H<sub>2</sub>L<sup>1</sup> = <i>N</i>-methyldiethanolamine and HL<sup>2</sup> = 2-(2-aminoethoxy)ethanol). It is worth noting that both <b>1-Gd</b> and <b>2-Gd</b> exhibit intramolecular antiferromagnetic interactions and show typical magnetocaloric effect behavior. At a magnetic field strength of 7 T and a temperature of 3 K, the values of the −Δ<i>S</i><sub>m</sub><sup>max</sup> are 33.65 J kg<sup>–1</sup> K<sup>–1</sup> for <b>1-Gd</b> and 25.22 J kg<sup>–1</sup> K<sup>–1</sup> for <b>2-Gd</b>. In addition, <b>1-Eu</b>, <b>1-Tb</b>, <b>2-Eu</b>, and <b>2-Tb</b> exhibit the characteristic luminescence of Eu<sup>III</sup> and Tb<sup>III</sup> ions, respectively. For <b>1-Tb</b>, tunable emission from green to red was achieved by adjusting the doping ratio of lanthanide ions to obtain heterometallic clusters <b>Tb</b><sub><i>x</i></sub><b>Eu</b><sub><b>9-x</b></sub>, offering the potential for high-fidelity optical barcode applications.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Crystal Growth & Design","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.cgd.4c01031","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
It is a challenging work to construct high-nuclear lanthanide nanoclusters with desirable magnetocaloric effects. To this end, a series of Ln9 nanoclusters with sandglass-like topological structures have been successfully synthesized under solvothermal conditions by using two different alcoholamine ligands and lanthanide (LnIII) salts, with the molecular formula [Ln9(L1)4(NO3)12(μ3-OH)8(μ4-OH)2(CH3CH2OH)4]·4.5CH3CH2OH·3Et3NH (LnIII = Gd (1-Gd), Eu (1-Eu), Tb (1-Tb)) and [Ln9(L2)8(NO3)8(μ3-OH)8(μ4-OH)2]·NO3 (LnIII = Gd (2-Gd), Eu (2-Eu), Tb (2-Tb)) (H2L1 = N-methyldiethanolamine and HL2 = 2-(2-aminoethoxy)ethanol). It is worth noting that both 1-Gd and 2-Gd exhibit intramolecular antiferromagnetic interactions and show typical magnetocaloric effect behavior. At a magnetic field strength of 7 T and a temperature of 3 K, the values of the −ΔSmmax are 33.65 J kg–1 K–1 for 1-Gd and 25.22 J kg–1 K–1 for 2-Gd. In addition, 1-Eu, 1-Tb, 2-Eu, and 2-Tb exhibit the characteristic luminescence of EuIII and TbIII ions, respectively. For 1-Tb, tunable emission from green to red was achieved by adjusting the doping ratio of lanthanide ions to obtain heterometallic clusters TbxEu9-x, offering the potential for high-fidelity optical barcode applications.
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.