The heteroanionic materials (HAMs) have attracted more and more attention because they can better balance the functional properties of materials. However, their rational structural design is still a great challenge. Here, by using the antiperovskite Ba₃S[GeS₄] as a template and calculating the tolerance factor (t) as a reference, eight heteroanionic oxychalcogenides with balanced properties were finally synthesized by a partially group-substitution method. Among them, Ba₃[CO₃][MQ₄] (M = Ge, Sn; Q = S, Se) are centrosymmetric (CS) crystals and realize optimization of band gaps and birefringence. For Ae₃[TO₃][SnOQ₃] (Ae = Sr, Ba; T = Si, Ge; Q = S, Se), thanks to the novel [TO₄SnQ₃] polyanionic groups for the regulation to the antiperovskite structures and the contributions to the nonlinear optical (NLO) properties, they achieve the structural transition from CS to noncentrosymmetry and accomplish an excellent balance among the critical performance parameters as the potential candidates for the infrared NLO materials, including phase-matchable behavior, wide band gaps (E_g = 3.26–3.95 eV), high laser damage threshold (LDT = 3.2–4.4 × AgGaS₂), suitable birefringence (Δn = 0.065–0.098@2090 nm) and sufficiently strong second-harmonic generation responses (about 0.6–0.9 × AgGaS₂). Moreover, benefiting from crystallization in the polar space groups, they exhibit ferroelectricity and piezoelectricity at room temperature. As far as we know, this is the first reported fully inorganic antiperovskite ferroelectric. These demonstrate that our strategy is desirable and can provide some unique insights into the development of HAMs or antiperovskite materials with specific functions or structures.

中文翻译：

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Ae3[TO3][SnOQ3]（Ae = Sr、Ba；T = Si、Ge；Q = S、Se）和 Ba3[CO3][MQ4]（M = Ge、Sn；Q = S、Se）：设计和系列杂阴离子反钙钛矿型硫族化物的合成


杂阴离子材料（HAMs）因其能够更好地平衡材料的功能特性而受到越来越多的关注。然而，其合理的结构设计仍然是一个巨大的挑战。在此，以反钙钛矿Ba ₃ S[GeS ₄ ]为模板，以计算耐受因子( t )为参考，通过部分基团取代法最终合成了8种性能平衡的杂阴离子硫属化物。其中，Ba ₃ [CO ₃ ][MQ ₄ ]（M = Ge，Sn；Q = S，Se）是中心对称（CS）晶体，实现带隙和双折射的优化。对于 Ae ₃ [TO ₃ ][SnOQ ₃ ]（Ae = Sr, Ba；T = Si, Ge；Q = S, Se），得益于新型 [TO ₄ SnQ ₃ ] 聚阴离子基团对反钙钛矿结构的调节以及对非线性光学（NLO）性能的贡献，它们实现了从CS到非中心对称的结构转变，并在作为红外NLO材料的潜在候选者的关键性能参数之间实现了良好的平衡，包括相位匹配行为、宽带隙( E _g = 3.26–3.95 eV)、高激光损伤阈值(LDT = 3.2–4.4 × AgGaS ₂ )、合适的双折射(Δ n = 0.065–0.098@2090 nm)和足够强的二次谐波产生响应(约0.6– 0.9 × AgGaS ₂ )。此外，得益于极性空间群的结晶，它们在室温下表现出铁电性和压电性。据我们所知，这是第一个报道的全无机反钙钛矿铁电体。 这些表明我们的策略是可取的，并且可以为开发具有特定功能或结构的 HAM 或反钙钛矿材料提供一些独特的见解。