Two new members in the quaternary Cs–Ag–As–S family with different arrangements of Ag–S and As–S asymmetric building units: syntheses, structures, and theoretical studies

Dongming Yan; Yu Xiao; Chang Liu; Peipei Hou; Wenxiang Chai; Hideo Hosono; Hua Lin; Yi Liu

doi:10.1039/D0DT01375G

Two new members in the quaternary Cs–Ag–As–S family with different arrangements of Ag–S and As–S asymmetric building units: syntheses, structures, and theoretical studies†

Dongming Yan,^a Yu Xiao,^b Chang Liu,^bc Peipei Hou,^b Wenxiang Chai,^d Hideo Hosono,^e Hua Lin

*^f and Yi Liu

*^b

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* Corresponding authors

^a School of Civil and Architectural Engineering, Zhejiang University, Hangzhou 310058, China

^b Institute for Composites Science Innovation (InCSI), School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
E-mail: liuyimse@zju.edu.cn

^c School of Materials Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China

^d College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China

^e Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

^f State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
E-mail: linhua@fjirsm.ac.cn

Abstract

New functional materials of As-based multinary chalcogenidometalates have received special attention due to their different oxidation states and flexible building blocks. In this work, two new quaternary thioarsenates(III), namely Cs₂Ag₂As₂S₅ (I) and Cs₃AgAs₄S₈ (II), have been obtained by a simple surfactant–thermal technique. Their structures were determined on the basis of single-crystal X-ray diffraction; compound I belongs to the triclinic space group P [1 with combining macron] (no. 2) [a = 7.49(2) Å, b = 9.30(2) Å, c = 9.94(2) Å, α = 63.28(3)°, β = 82.11(3)°, γ = 87.78(3)°, V = 612.4(2) Å³ and Z = 2], whereas compound II crystallizes in the monoclinic space group C2/c (no. 12) [a = 27.76(6) Å, b = 6.98(2) Å, c = 19.68(4) Å, β = 109.85(3)°, V = 3586.7(2) Å³ and Z = 8]. Both structures are shown to feature two-dimensional (2D) layers with different arrangements of Ag–S and As–S asymmetric building units (ABUs). In compound I, the layer is constructed from vertex-sharing dimeric [As₂S₅] units linked by tetrameric [Ag₄S₈] moieties. The layered structure in compound II is formed by 2₁ helical chains based on [As₄S₉] groups which are further interconnected by tetrahedral [AgS₄] chains. The analysis of the quaternary X–Ag–As–S (X = cations) system shows that various combination ways of Ag–S and As–S ABUs in these sulfides can be attributed to the cation-cation repulsion and stereochemically active lone-pair effect. The UV-vis/NIR absorption spectrum indicates that the optical band energy (E_g) of compounds I and II is 2.48 eV and 2.24 eV, respectively. Moreover, theoretical calculations indicate that the As–S and Ag–S bonding states determine the optical properties of the title compounds. This work not only enriches the structural chemistry of thioarsenates, but also opens up a new avenue for exploring novel multinary chalcogenidometalates.

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Two new members in the quaternary Cs–Ag–As–S family with different arrangements of Ag–S and As–S asymmetric building units: syntheses, structures, and theoretical studies†

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Two new members in the quaternary Cs–Ag–As–S family with different arrangements of Ag–S and As–S asymmetric building units: syntheses, structures, and theoretical studies

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