Issue 14, 2022
From the journal:

Inorganic Chemistry Frontiers

Structural dimension modulation in a new oxysulfide system of Ae2Sb2O2S3 (Ae = Ca and Ba)†

Ruiqi Wang,a   Yantao Zhao,a   Xian Zhang ORCID logo *b  and  Fuqiang Huang ORCID logo *ac  

* Corresponding authors

a Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
E-mail: huangfq@pku.edu.cn

b Qian Xuesen Laboratory of Space Technology, China Academy of Space Technology, Beijing, 100094 P. R. China
E-mail: zhangxian@qxslab.cn

c State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China

Abstract

Inspired by the abundant structural diversity and potential applications of Sb-based oxysulfides, two new compounds with the same stoichiometry, Ae2Sb2O2S3 (Ae = Ca, Ba), were successfully synthesized via solid state reactions. Both crystallize in the C2/c space group (no. 15) of a monoclinic system, however, possess different structural dimensions induced by different sizes of template alkaline-earth ions. Ca2Sb2O2S3 is composed of one-dimensional anionic [Sb2O2S3]4− chains isolated by Ca2+ ions, while Ba2Sb2O2S3 consists of zero-dimensional anionic [Sb2O2S3]4− clusters separated by Ba2+ ions. Higher structural dimension endows the 1D Ca2Sb2O2S3 with a higher melting point (m.p. = 720 °C) and a narrower band gap (Eg = 2.36 eV), compared with the m.p. = 692 °C and Eg = 2.78 eV of Ba2Sb2O2S3. Both exhibit interesting photoluminescence properties with multiemission characteristics. DFT calculations reveal that the band edges of Ae2Sb2O2S3 are mainly composed of Sb−S bond orbitals, while O 2p orbitals also contribute to the valence band maximum of Ba2Sb2O2S3.

Graphical abstract: Structural dimension modulation in a new oxysulfide system of Ae2Sb2O2S3 (Ae = Ca and Ba)

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Article information

DOI
https://doi.org/10.1039/D2QI00698G
Article type
Research Article
Submitted
01 Apr 2022
Accepted
27 May 2022
First published
31 May 2022

Inorg. Chem. Front., 2022,9, 3552-3558

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Structural dimension modulation in a new oxysulfide system of Ae2Sb2O2S3 (Ae = Ca and Ba)

R. Wang, Y. Zhao, X. Zhang and F. Huang, Inorg. Chem. Front., 2022, 9, 3552 DOI: 10.1039/D2QI00698G

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