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Syntheses, Structures and Magnetic Properties of Novel Tetrameric Ln2Mn2 and Ring-like Ln4Mn4 Clusters

Abstract

Three tetrameric Ln-Mn clusters with formulae as [Ln2Mn2(hmp)6(NO3)4(H2O)4](ClO4)2·xH2O (Ln = Y, x = 1 (1); Ln = Gd, x = 3 (2); Ln = Dy, x = 4 (3)) and three ring-like Ln-Mn clusters [Ln4Mn4(hmp)4(L)4(H2L)4(CH3CN)(H2O)7](NO3)4·H2O (Ln = Y (4), Gd (5), Dy (6), hmpH = 2-(Hydroxymethyl)pyridine, H3L = 2,2-Bis(hydroxymethyl)butyric acid) have been synthesized in the presence of alcohol ligands. Single X-ray analysis revealed that compounds 1–3 exhibited a zigzag metal core unit of [Y2Mn2(hmp)6]6+ ([Y-Mn-Mn-Y]), which can form a three-dimensional (3D) metal framework via - stacking. Compounds 4–6 formed the ring-shaped metal skeleton of Ln4Mn4 and displayed an ideal metal arrangement with the alternating Ln and Mn ions, which was consistent with the predicted metal arrangement of [-Ln-M-Ln-M-] with weak magnetic interaction. Magnetic investigation showed that 1 displayed significant ferromagnetic interaction and 2–6 displayed dominant antiferromagnetic interaction. Magnetic calculation showed that in 2 the Gd···Mn and Mn···Mn presented an antiferromagnetic interaction and a weak ferromagnetic interaction, respectively. For 5, the Gd···Mn showed a weak antiferromagnetic interaction and the Gd···Gd showed a much weaker ferromagnetic interaction due to the spacing of Gd(III) ions by Mn(III) ions which effectively weaken the antiferromagnetic coupling between Gd3+ ions, in addition, magnetothermal studies showed that 5 displayed magnetic entropy changes of 15.5 J kg–1 K–1 at 3.5 K for ΔH = 7 T.

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Supplementary files

Article information


Submitted
28 Mar 2020
Accepted
19 May 2020
First published
20 May 2020

New J. Chem., 2020, Accepted Manuscript
Article type
Paper

Syntheses, Structures and Magnetic Properties of Novel Tetrameric Ln2Mn2 and Ring-like Ln4Mn4 Clusters

J. Yin, C. Chen, G. Zhuang, J. Zheng, X. Zheng and F. Shao, New J. Chem., 2020, Accepted Manuscript , DOI: 10.1039/D0NJ01517B

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