Surface ligands play important roles in controlling the size and shape of metal nanoparticles and their surface properties. In this work, we demonstrate that the use of bulky thiolate ligands, along with halides, as the surface capping agent promotes the formation of plasmonic multiple-twinned Ag nanoparticles with high surface reactivities. The title nanocluster [Ag₁₄₁X₁₂(S-Adm)₄₀]³⁺ (where X = Cl, Br, I; S-Adm = 1-adamantanethiolate) has a multiple-shell structure with an Ag₇₁ core protected by a shell of Ag₇₀X₁₂(S-Adm)₄₀. The Ag₇₁ core can be considered as 20 frequency-two Ag₁₀ tetrahedra fused together with a dislocation that resembles multiple-twinning in nanoparticles. The nanocluster has a strong plasmonic absorption band at 460 nm. Because of the bulkiness of S-Adm, the nanocluster has a low surface thiolate coverage and thus unusually high surface reactivities toward exchange reactions with different ligands, including halides, phenylacetylene and thiols. The cluster can be made water-soluble by metathesis with water-soluble thiols, thereby creating new functionalities for potential bioapplications.

中文翻译：

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庞大的表面配体促进[Ag ₁₄₁ X ₁₂（S-Adm）₄₀ ] ³⁺（X = Cl，Br，I）纳米团簇的表面反应性：多重孪生纳米粒子的模型

表面配体在控制金属纳米颗粒的大小和形状及其表面性质方面起着重要作用。在这项工作中，我们证明了使用大体积的硫醇盐配体以及卤化物作为表面覆盖剂可以促进具有高表面反应性的等离激元多重孪生Ag纳米颗粒的形成。标题纳米簇[Ag ₁₄₁ X ₁₂（S-Adm）₄₀ ] ³⁺（其中X = Cl，Br，I； S-Adm = 1-金刚烷硫醇盐）具有多壳结构，其中Ag ₇₁核被壳保护Ag ₇₀ X ₁₂（S-Adm）₄₀的含量。Ag ₇₁磁芯可视为20个频率，两个Ag ₁₀四面体与位错融合在一起，而位错类似于纳米颗粒中的多重孪晶。纳米簇在460 nm处具有很强的等离子体吸收带。由于S-Adm的体积大，纳米团簇具有低的表面硫醇盐覆盖率，因此在与包括卤化物，苯乙炔和硫醇的不同配体的交换反应中具有异常高的表面反应性。簇可以通过与水溶性硫醇的复分解而变成水溶性的，从而为潜在的生物应用创造了新的功能。