Searching for the coexistence of a wide energy gap (E_g > 3.5 eV) and a large second-harmonic generation efficiency (d_ij > 0.6 × AgGaS₂) for noncentrosymmetric (NCS) materials in the IR nonlinear optical (NLO) field is highly desirable but still remains a huge challenge because of the incompatibility between them. To address this issue, a new salt-inclusion chalcogenide, namely, [Ba₄Cl₂][ZnGa₄S₁₀], has been designed and successfully synthesized by a chemical multisubstitution approach with chalcopyrite-type AgGaS₂ (AGS) as the template. [Ba₄Cl₂][ZnGa₄S₁₀] adopts the NCS space group I4̅ with lattice dimensions a = b = 8.2882(4) Å, c = 15.1693(9) Å, V = 1042.04(9) ų, and Z = 2. The structure is constructed with corner-sharing supertetrahedral [Ga₄S₁₀]^8– clusters (T₂) and [ZnS₄]^6– tetrahedra (T₁) to form a three-dimensional open [ZnGa₄S₁₀]^6– diamond-like framework, which is further interpenetrated with charge-balanced Ba²⁺ and Cl^–. Remarkably, the title compound not only retains the large d_ij (1.1 × AGS) but also possesses a wide E_g (ca. 3.85 eV) corresponding to an ultrahigh laser-induced damage threshold (LIDT = 51 × AGS), demonstrating that it achieves the key indexes as a promising IR-NLO candidate. Furthermore, density functional theory (DFT) analysis has assisted the comprehension of the structure–property relationships. Both the experimental and DFT calculation results indicate the practicability of such a chemical multisubstitution approach to design excellent IR-NLO materials, that is, breaking the incompatibility between a wide E_g and a large d_ij.

中文翻译：

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含盐硫族化物[Ba ₄ Cl ₂ ] [ZnGa ₄ S ₁₀ ]：AgGaS ₂衍生的具有优异综合性能的红外非线性光学材料的合理设计

在红外非线性光学（NLO）领域中，对于非中心对称（NCS）材料，寻找宽能隙（E _g > 3.5 eV）和大二次谐波产生效率（d _ij > 0.6×AgGaS ₂）的共存是非常重要的理想，但由于它们之间的不兼容，仍然是一个巨大的挑战。为了解决这个问题，以黄铜矿型AgGaS ₂（AGS）为模板，通过化学多取代法设计并成功合成了一种新的含盐硫族化物[Ba ₄ Cl ₂ ] [ZnGa ₄ S ₁₀ ]。。[Ba ₄ Cl ₂ ] [ZnGa₄ š ₁₀ ]采用NCS空间群我4晶格尺寸一个= b = 8.2882（4），C ^ = 15.1693（9）埃，V = 1042.04（9）埃³，与Ž = 2的结构被构造具有角共享超四面体[Ga ₄ S ₁₀ ] ^8–团簇（T ₂）和[ZnS ₄ ] ^6–四面体（T ₁）形成三维开放[ZnGa ₄ S ₁₀ ] ^6–金刚石状框架，其与电荷平衡的Ba进一步互穿²⁺和Cl ^- 。值得注意的是，标题化合物不仅保留了较大的d _ij（1.1×AGS），而且具有较宽的E _g（约3.85 eV），对应于超高激光诱导的损伤阈值（LIDT = 51×AGS），表明它作为有希望的IR-NLO候选者，获得了关键指标。此外，密度泛函理论（DFT）分析有助于理解结构与属性之间的关系。实验结果和DFT计算结果均表明，这种化学多取代方法可用于设计优异的IR-NLO材料，即打破了多种材料之间的不相容性。E _g和大d _ij。