Atom-by-Atom Evolution of the Same Ligand-Protected Au21, Au22, Au22Cd1, and Au24 Nanocluster Series,Journal of the American Chemical Society

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Atom-by-Atom Evolution of the Same Ligand-Protected Au21, Au22, Au22Cd1, and Au24 Nanocluster Series
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-11-10 , DOI: 10.1021/jacs.0c09110
Yingwei Li ₁ , Michael J Cowan ₂ , Meng Zhou ₃ , Tian-Yi Luo ₄ , Yongbo Song ₁ , He Wang ₃ , Nathaniel L Rosi ₄ , Giannis Mpourmpakis ₂ , Rongchao Jin ₁

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Atom-by-atom manipulation on metal nanoclusters (NCs) has long been desired, as the resulting series of NCs can provide insightful understanding of how a single atom affects the structure and properties as well as the evolution with size. Here, we report crystallizations of Au22(SAdm)16 and Au22Cd1(SAdm)16 (SAdm = adamantanethiolate) which link up with Au21(SAdm)15 and Au24(SAdm)16 NCs and form an atom-by-atom evolving series protected by the same ligand. Structurally, Au22(SAdm)16 has an Au3(SAdm)4 surface motif which is longer than the Au2(SAdm)3 on Au21(SAdm)15, whereas Au22Cd1(SAdm)16 lacks one staple Au atom compared to Au24(SAdm)16 and thus the surface structure is reconstructed. A single Cd atom triggers the structural transition from Au22 with a 10-atom bioctahedral kernel to Au22Cd1 with a 13-atom cuboctahedral kernel, and correspondingly, the optical properties are dramatically changed. The photoexcited carrier lifetime demonstrates that the optical properties and excited state relaxation are highly sensitive at the single atom level. By contrast, little change in both ionization potential and electron affinity is found in this series of NCs by theoretical calculations, indicating the electronic properties are independent of adding a single atom in this series. The work provides a paradigm that the NCs with continuous metal atom numbers are accessible and crystallizable when meticulously designed, and the optical properties are more affected at the single atom level than the electronic properties.

中文翻译：

相同配体保护的 Au21、Au22、Au22Cd1 和 Au24 纳米团簇系列的原子演化

长期以来人们一直希望对金属纳米团簇（NC）进行原子对原子的操纵，因为由此产生的一系列NC可以提供对单个原子如何影响结构和性质以及尺寸演变的深刻理解。在这里，我们报告了 Au22(SAdm)16 和 Au22Cd1(SAdm)16 (SAdm = 金刚烷硫醇) 的结晶，它们与 Au21(SAdm)15 和 Au24(SAdm)16 NC 连接并形成受保护的逐个原子演化系列相同的配体。在结构上，Au22(SAdm)16 具有一个 Au3(SAdm)4 表面基序，该基序比 Au21(SAdm)15 上的 Au2(SAdm)3 更长，而与 Au24(SAdm) 相比，Au22Cd1(SAdm)16 缺少一个主键 Au 原子如图16所示，从而重建表面结构。单个Cd原子触发了从具有10个原子的双八面体内核的Au22到具有13个原子的立方八面体内核的Au22Cd1的结构转变，相应地，光学性质发生了巨大的变化。光激发载流子寿命表明光学性质和激发态弛豫在单原子水平上是高度敏感的。相比之下，通过理论计算发现该系列NC的电离势和电子亲和力几乎没有变化，表明该系列NC的电子性质与添加单个原子无关。这项工作提供了一个范例，即经过精心设计，具有连续金属原子数的NC是可接近和可结晶的，并且光学性能在单原子水平上比电子性能受到更大的影响。

更新日期：2020-11-10

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