C2O42−-templated cage-shaped Ln28 (Ln = Gd, Eu) nanoclusters with magnetocaloric effect and luminescence

Qin Wang; Sheng-Hui Lu; Ling-Xi Xu; Ji-Lei Wang; Ya-Ting Yu; Xu Bai; Hua Mei; Yan Xu

doi:10.1039/D3QI00743J

C₂O₄²⁻-templated cage-shaped Ln₂₈ (Ln = Gd, Eu) nanoclusters with magnetocaloric effect and luminescence†

Qin Wang,^a Sheng-Hui Lu,^a Ling-Xi Xu,^b Ji-Lei Wang,

^a Ya-Ting Yu,^a Xu Bai,^a Hua Mei^a and Yan Xu

*^a

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* Corresponding authors

^a College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, P. R. China
E-mail: yanxu@njtech.edu.cn

^b College of Software, Jilin University, Changchun 130012, P. R. China

Abstract

The assembly of high-nuclearity lanthanide nanoclusters with favourable magnetocaloric effects suffers from a significant challenge. Herein, two outstanding examples of cage-shaped nanoclusters, namely, [Ln₂₈(IN)₂₅(C₂O₄)₆(HCOO)(μ₃-OH)₃₆(μ₂-OH)₂(H₂O)₃₆]·8Br·xH₂O (Ln = Gd and Eu; x = 21, abbreviated as Gd₂₈; x = 17, abbreviated as Eu₂₈, HIN = isonicotinic acid; H₂C₂O₄ = oxalic acid) have been triumphantly designed and constructed under hydrothermal conditions. The crystallographic study revealed that the aesthetically pleasing triangle-shaped Gd₁₂ subunit and Gd₁₆ subunit built separately from four Gd₃ units and four Gd₄ units, respectively, are shaped into an unprecedented cage-shaped configuration. Prominently, six small and simple C₂O₄²⁻ anions generated via the in situ reaction of HIN are faultlessly anchored in the cage-shaped framework. Furthermore, the existence of abundant Gd^III ions impart Gd₂₈ with a captivating magnetic entropy change (−ΔS^max_m = 37.5 J kg⁻¹ K⁻¹) at 2.0 K for ΔH = 7.0 T.

This article is part of the themed collection: 2023 Inorganic Chemistry Frontiers HOT articles

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Article information

DOI: https://doi.org/10.1039/D3QI00743J
Article type: Research Article
Submitted: 24 Apr 2023
Accepted: 07 Jun 2023
First published: 08 Jun 2023

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Inorg. Chem. Front., 2023,10, 4109-4116

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C₂O₄²⁻-templated cage-shaped Ln₂₈ (Ln = Gd, Eu) nanoclusters with magnetocaloric effect and luminescence

Q. Wang, S. Lu, L. Xu, J. Wang, Y. Yu, X. Bai, H. Mei and Y. Xu, Inorg. Chem. Front., 2023, 10, 4109 DOI: 10.1039/D3QI00743J

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