We report two anion‐templated Ag₄₀ clusters, [Ag₄₀(E)₄(SO₄){S₂P(OEt)₂}₂₄](PF₆)₆ (E = S, 1; Se, 2). The anionic templates were generated in situ from the decomposition of dithiophosphate (dtp) ligands. The extrusion of sulfur undergoes disproportionation reactions to generate sulfide and sulfate anions, which provide the source of templates in the subsequent cluster assembly reactions. Two Ag₄₀ clusters display high similarity in their structures. The sulfide (selenide) anions and the central sulfate anion reveal a six‐coordinate and a rare dodecametallic dodecaconnective pattern, respectively. Four near‐equivalent [Ag₁₀(E){S₂P(OEt)₂}₆]²⁺ motifs were assembled via the connection of central sulfate anion to construct Ag₄₀ clusters. The cluster cation, [Ag₄₀(E)₄(SO₄){S₂P(OEt)₂}₂₄]⁶⁺, displayed in T symmetry, is unprecedented in anion‐templated silver clusters.

中文翻译：

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杂阴离子组装的T对称40核银簇

我们报告了两个以阴离子为模板的Ag ₄₀簇，[Ag ₄₀（E）₄（SO ₄）{S ₂ P（OEt）₂ } ₂₄ ]（PF ₆）₆（E = S，1 ; Se，2）。阴离子模板是由二硫代磷酸酯（dtp）配体的分解原位生成的。硫的挤出经历歧化反应以生成硫化物和硫酸根阴离子，这在随后的簇组装反应中提供了模板的来源。两个Ag ₄₀集群在结构上显示出高度相似性。硫化物（硒化物）阴离子和中心硫酸盐阴离子分别显示六坐标和稀有的十二金属十二键连接模式。通过中央硫酸根阴离子的连接，组装了四个接近当量的[Ag ₁₀（E）{S ₂ P（OEt）₂ } ₆ ] ²⁺基序，以构建Ag ₄₀簇。以T对称性显示的簇阳离子[Ag ₄₀（E）₄（SO ₄）{S ₂ P（OEt）₂ } ₂₄ ] ⁶⁺在阴离子模板的银簇中是空前的。