Sandglass-like Ln9 Nanoclusters with Magnetocaloric Effect and Lanthanide-Centered Luminescence

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-09-16 DOI:10.1021/acs.cgd.4c01031

Tiantian Wang, Hao Wang, Wenbin Sun

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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 (Ln^III) salts, with the molecular formula [Ln₉(L¹)₄(NO₃)₁₂(μ₃-OH)₈(μ₄-OH)₂(CH₃CH₂OH)₄]·4.5CH₃CH₂OH·3Et₃NH (Ln^III = Gd (1-Gd), Eu (1-Eu), Tb (1-Tb)) and [Ln₉(L²)₈(NO₃)₈(μ₃-OH)₈(μ₄-OH)₂]·NO₃ (Ln^III = 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 −ΔS_m^max 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 Eu^III and Tb^III 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 Tb_xEu_9-x, offering the potential for high-fidelity optical barcode applications.

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具有磁致效应和以镧系元素为中心的发光特性的类砂玻璃 Ln9 纳米团簇

构建具有理想磁ocaloric效应的高核镧系纳米团簇是一项具有挑战性的工作。为此，我们利用两种不同的醇胺配体和镧系元素（LnIII）盐，在溶热条件下成功合成了一系列具有沙漏状拓扑结构的 Ln9 纳米团簇，分子式为[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)）和 [Ln9(L2)8(NO3)8(μ3-OH)8(μ4-OH)2]-NO3 （LnIII = Gd (2-Gd)、Eu（2-Eu）、Tb（2-Tb））（H2L1 = N-甲基二乙醇胺，HL2 = 2-（2-氨基乙氧基）乙醇）。值得注意的是，1-钆和 2-钆都表现出分子内反铁磁相互作用，并显示出典型的磁致效应行为。在磁场强度为 7 T、温度为 3 K 的条件下，1-钆的-ΔSmmax 值为 33.65 J kg-1 K-1，2-钆的-ΔSmmax 值为 25.22 J kg-1 K-1。此外，1-Eu、1-Tb、2-Eu 和 2-Tb 分别显示出 EuIII 离子和 TbIII 离子的发光特征。就 1-Tb 而言，通过调整镧系离子的掺杂比例，获得了 TbxEu9-x 异金属团簇，从而实现了从绿色到红色的可调发射，为高保真光学条形码应用提供了潜力。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

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.