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Issue 4, 2017
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New metal chalcogenides found in MnN−1(Gd2−xInx)SN+2 (N = 3, 4, 5): syntheses, structures, and magnetic properties

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Abstract

Three new metal chalcogenides have been identified in MnN−1(Gd2−xInx)SN+2 with N = 3, 4, and 5 via a flux-growth synthesis. All compounds crystallize in the same space group of orthorhombic Cmcm with cell constants: Mn2GdInS5 (1), a = 3.789(1) Å, b = 12.411(1) Å, and c = 15.489(1) Å; Mn3Gd2S6 (2), a = 3.778(1) Å, b = 12.505(2) Å, and c = 19.114(2) Å; Mn4Gd2S7 (3), a = 3.769(1) Å, b = 12.466(2) Å, and c = 22.289(3) Å. Compounds 1–3 form a homologous series through the modulation of the MnS unit, whose structures represent a complete system of the corresponding lillianites (N1,N2L) of 3,3L, 4,4L and 5,5L. The gradually wider slabs formed in the series result in a monotonic increase along the c dimensions from 1 to 3. Crystal 3 is the first to achieve a predicted structure of 5,5L. Mn2GdInS5 (1) displays a weak antiferromagnetic (AFM) ordering at 10 K and the Weiss constant (θ) of −0.76 K. Mn2Gd1.5In0.5S5 (1a), an isostructure of 1, shifts the AFM transition temperature to 12 K and possesses a slightly larger θ constant of −6.06 K. Mn4Gd2S7 (3), featuring the thickest slabs in this series, shows a significant antiferromagnetic behavior beginning at a high temperature of 70 K and has a largest θ constant of −40.25 K. A small amount of impurity α-Gd2S3 with an AFM transition temperature around 4 K was characterized in sample 3, which does not interfere with the magnetic ordering of 3 at much higher temperatures. These magnetic chalcogenides display band gaps of 1.66 eV for 1, 1.75 eV for 1a, and 1.44 eV for 3.

Graphical abstract: New metal chalcogenides found in MnN−1(Gd2−xInx)SN+2 (N = 3, 4, 5): syntheses, structures, and magnetic properties

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Article information


Submitted
18 Nov 2016
Accepted
14 Dec 2016
First published
15 Dec 2016

Dalton Trans., 2017,46, 1228-1236
Article type
Paper

New metal chalcogenides found in MnN−1(Gd2−xInx)SN+2 (N = 3, 4, 5): syntheses, structures, and magnetic properties

I. C. Liang, C. Y. Weng, C. Huang, C. K. Chang, H. S. Sheu, J. G. Lin and K. F. Hsu, Dalton Trans., 2017, 46, 1228
DOI: 10.1039/C6DT04382H

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