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Article Dans Une Revue Inorganic Chemistry Année : 2023

Revisiting the Crystal Structure of Layered Oxychalcogenides Ln2O2S2 (Ln = La, Pr, and Nd)

Résumé

La2O2S2 was recently used as a precursor to prepare either a new metastable form of La2O2S by de-insertion of half of sulfur atoms of (S2) dimers or quaternary compounds by insertion of a coinage metal (e.g., La2O2Cu2S2). A strong structural relationship exists between the polysulfide precursor and the synthesized products, which highlights the topochemical nature of these reactions. Nevertheless, the crystal structure of the precursor material is still a matter of debate. Namely, several structural models were reported so far in the literature with different space groups and/or crystal systems. All these models were built upon infinite [Ln2O2] slabs separated from each other by a flat sul f u r layer of (S2) dumbbells. Nevertheless, all (S2) dimer s within a given sul f u r layer may rotate in phase by 90 degrees compared to the orientation along the stacking axis. This leads to some imbroglio and much confusion in the description of structural arrangement of Ln2O2S2 materials. Herein, the crystal structures of La2O2S2 and its Pr and Nd variants are revisited. We propose an alternative model that reconciles pre-existing structural descriptions of Ln2O2S2 (Ln = La, Pr, and Nd) materials and highlights the strong dependency of the degree of long-range ordering of the sulfur layers on the synthesis conditions.

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Chimie
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Dates et versions

hal-04126158 , version 1 (13-11-2023)

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Louis-Béni Mvélé, Shunsuke Sasaki, Camille Latouche, Philippe Deniard, Etienne Janod, et al.. Revisiting the Crystal Structure of Layered Oxychalcogenides Ln2O2S2 (Ln = La, Pr, and Nd). Inorganic Chemistry, 2023, 62 (19), pp.7264-7272. ⟨10.1021/acs.inorgchem.3c00147⟩. ⟨hal-04126158⟩
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