Structural Isomerism in Bimetallic Ag20Cu12 Nanoclusters,Journal of the American Chemical Society

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Structural Isomerism in Bimetallic Ag20Cu12 Nanoclusters
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-09-18 , DOI: 10.1021/jacs.4c06832
Guocheng Deng _{1,

2} , Sami Malola ₃ , Taeyoung Ki _{1,

2} , Xiaolin Liu _{1,

2} , Seungwoo Yoo _{1,

2} , Kangjae Lee _{1,

2} , Megalamane S Bootharaju _{1,

2} , Hannu Häkkinen ₃ , Taeghwan Hyeon _{1,

2}

Affiliation

Structural isomers of atomically precise metal nanoclusters are highly sought after for investigating structure–property relationships in nanostructured materials. However, they are extremely rare, particularly those of alloys, primarily due to the challenges in their synthesis and structural characterization. Herein, for the first time, a pair of bimetallic isomeric AgCu nanoclusters has been controllably synthesized and structurally characterized. These two isomers share an identical molecular formula, Ag₂₀Cu₁₂(C≡CR)₂₄ (denoted as Ag₂₀Cu₁₂-1 and Ag₂₀Cu₁₂-2; HC≡CR is 3,5-bis(trifluoromethyl)phenylacetylene). Single-crystal X-ray diffraction data analysis revealed that Ag₂₀Cu₁₂-1 possesses an Ag₁₇Cu₄ core composed of two interpenetrating hollow Ag₁₁Cu₂ structures. This core is stabilized by four different types of surface motifs: eight –C≡CR, one Cu(C≡CR)₂, one Ag₃Cu₃(C≡CR)₆, and two Cu₂(C≡CR)₄ units. Ag₂₀Cu₁₂-2 features a bitetrahedron Ag₁₄ core, which is stabilized by three Ag₂Cu₄(C≡CR)₈ units. Interestingly, Ag₂₀Cu₁₂-2 undergoes spontaneous transformation to Ag₂₀Cu₁₂-1 in the solution-state. Density functional theory calculations explain the electronic and optical properties and confirm the higher relative stability of Ag₂₀Cu₁₂-1 compared to Ag₂₀Cu₁₂-2. The controlled synthesis and structural isomerism of alloy nanoclusters presented in this work will stimulate and broaden research on nanoscale isomerism.

中文翻译：

双金属 Ag20Cu12 纳米团簇中的结构异构

原子精确金属纳米团簇的结构异构体在研究纳米结构材料中的结构-性能关系方面备受追捧。然而，它们极为罕见，尤其是合金，主要是因为它们的合成和结构表征存在挑战。在此，首次可控合成了一对双金属异构体 AgCu 纳米团簇并对其进行了结构表征。这两种异构体具有相同的分子式，即 Ag₂₀Cu₁₂（C≡CR）₂₄（表示为 Ag₂₀Cu_12-1 和 Ag₂₀Cu_12-2;HC≡CR 是 3,5-双（三氟甲基）苯乙炔）。单晶 X 射线衍射数据分析表明，Ag₂₀Cu_12-1 具有由两个互穿的空心 Ag₁₁Cu₂ 结构组成的 Ag₁₇Cu₄ 核心。该核心由四种不同类型的表面基序稳定：八个 –C≡CR、一个 Cu（C≡CR）₂、一个 Ag₃、Cu₃（C≡CR）₆ 和两个 Cu₂（C≡CR）₄ 单元。Ag₂₀Cu_12-2 具有双四面体 Ag₁₄ 核心，由三个 Ag₂Cu₄（C≡CR）₈ 单元稳定。有趣的是，Ag₂₀Cu_12-2 在溶液状态下自发转变为 Ag₂₀Cu_12-1。密度泛函理论计算解释了电子和光学特性，并证实了 Ag₂₀Cu_12-1 的相对稳定性高于 Ag₂₀Cu_12-2。这项工作中提出的合金纳米团簇的受控合成和结构异构性将刺激和拓宽对纳米级异构的研究。

更新日期：2024-09-18

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