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 (E_g = 2.36 eV), compared with the m.p. = 692 °C and E_g = 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.

中文翻译：

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Ae2Sb2O2S3 (Ae = Ca 和 Ba) 新氧硫化物体系中的结构尺寸调制

受 Sb 基氧硫化物丰富的结构多样性和潜在应用的启发，通过固态反应成功合成了两种化学计量相同的新化合物 Ae ₂ Sb ₂ O ₂ S ₃ (Ae = Ca, Ba) 。两者都在单斜晶系的C 2/ c空间群（第 15 号）中结晶，然而，具有由不同尺寸的模板碱土离子引起的不同结构尺寸。Ca ₂ Sb ₂ O ₂ S ₃由一维阴离子[Sb ₂ O ₂ S ₃ ]组成⁴⁻链由Ca ²⁺离子分离，而Ba ₂ Sb ₂ O ₂ S ₃由零维阴离子[Sb ₂ O ₂ S ₃ ] ⁴⁻簇由Ba ²⁺离子分离。与 mp = 692 °C 和E _g相比，更高的结构尺寸赋予一维 Ca ₂ Sb ₂ O ₂ S ₃更高的熔点 (mp = 720 °C) 和更窄的带隙 ( E _g = 2.36 eV) = 2.78 eV Ba ₂ Sb ₂ O₂秒₃。两者都表现出有趣的光致发光特性和多发射特性。DFT计算表明Ae ₂ Sb ₂ O ₂ S ₃的带边主要由Sb-S键轨道组成，而O 2p 轨道也对Ba ₂ Sb ₂ O ₂ S ₃的价带最大值有贡献。