A prototypical thiolate (RS)-protected gold cluster [Au₂₅(SR)₁₈]⁻ has high stability due to specific geometric and electronic structures: an icosahedral (I_h) Au₁₃ core with a closed electronic shell containing eight electrons is completely protected by six units of Au₂(SR)₃. Nevertheless, collisional excitation of [Au₂₅(SR)₁₈]⁻ in a vacuum induces the sequential release of Au₄(SR)₄ to form [Au₂₁(SR)₁₄]⁻ and [Au₁₇(SR)₁₀]⁻ both containing eight electrons. To answer a naive question of whether these fragments bear an I_h Au₁₃(8e) core, the geometrical structures of [Au₂₁(SC₃H₇)₁₄]⁻ and [Au₁₇(SC₃H₇)₁₀]⁻ in the gas phase were examined by the combination of anion photoelectron spectroscopy and density functional theory (DFT) calculation of simplified models of [Au₂₁(SCH₃)₁₄]⁻ and [Au₁₇(SCH₃)₁₀]⁻. We concluded that [Au₂₁(SC₃H₇)₁₄]⁻ retains a slightly distorted I_h Au₁₃(8e) core, while [Au₁₇(SC₃H₇)₁₀]⁻ has an amorphous Au₁₃ core composed of triangular Au₃, tetrahedral Au₄, and prolate Au₇ units. DFT calculations on putative species [Au₁₉(SCH₃)₁₂]⁻ and [Au₁₈(SCH₃)₁₁]⁻ suggested that the I_h Au₁₃(8e) core undergoes dramatic structural deformation due to mechanical stress from μ₂ ligation of only one RS.

中文翻译：

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具有八个电子的 [Au21(SR)14]− 和 [Au17(SR)10]− 的气相结构：它们可以支持二十面体 Au13 核吗？

原型硫醇盐 (RS) 保护的金簇 [Au ₂₅ (SR) ₁₈ ] ⁻由于特定的几何和电子结构而具有高稳定性：具有包含八个电子的封闭电子壳的二十面体 ( I _h ) Au ₁₃核受到完全保护由六个单位的Au ₂ (SR) ₃组成。然而，真空中[Au ₂₅ (SR) ₁₈ ] ^{-的碰撞激发会导致 Au} ₄ (SR) ₄依次释放，形成 [Au ₂₁ (SR) ₁₄ ] ^-和 [Au ₁₇ (SR) ₁₀ ] ^-两者含有八个电子。为了回答这些碎片是否具有I _h Au ₁₃ (8e) 核心的简单问题，[Au ₂₁ (SC ₃ H ₇ ) ₁₄ ] ^-和 [Au ₁₇ (SC ₃ H ₇ ) ₁₀ ] ^-的几何结构在通过结合阴离子光电子能谱和密度泛函理论（DFT）计算[Au ₂₁ (SCH ₃ ) ₁₄ ] ^-和[Au ₁₇ (SCH ₃ ) ₁₀ ] ^-的简化模型来检查气相。我们得出结论，[Au ₂₁ (SC ₃ H ₇ ) ₁₄ ] ⁻保留了稍微扭曲的I _h Au ₁₃ (8e) 核，而 [Au ₁₇ (SC ₃ H ₇ ) ₁₀ ] ⁻具有由三角形组成的非晶 Au ₁₃核。 Au ₃、四面体 Au ₄和扁长形 Au ₇单元。对假定物质 [Au ₁₉ (SCH ₃ ) ₁₂ ] ^-和 [Au ₁₈ (SCH ₃ ) ₁₁ ] ^-的 DFT 计算表明，由于 μ ₂连接产生的机械应力， I _h Au ₁₃ (8e) 核心经历了剧烈的结构变形。只有一个RS。