Electronic state modulation of Ag30 nanoclusters within a ring-shaped polyoxometalate,Nanoscale

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Electronic state modulation of Ag30 nanoclusters within a ring-shaped polyoxometalate
Nanoscale ( IF 5.8 ) Pub Date : 2024-09-10 , DOI: 10.1039/d4nr02547d
Daiki Yanai ₁ , Kentaro Yonesato ₁ , Soichi Kikkawa ₂ , Seiji Yamazoe ₂ , Kazuya Yamaguchi ₁ , Kosuke Suzuki ₁

Affiliation

Atomically precise Ag nanoclusters display distinctive properties that are dictated by their structures and electronic states. However, manipulating the electronic states of Ag nanoclusters is challenging owing to their inherent instability and susceptibility to undesired structural changes, decomposition, and aggregation. Recently, we reported the synthesis of a body-centered cubic {Ag₃₀}²²⁺ nanocluster encapsulated within a ring-shaped polyoxometalate (POM) [P₈W₄₈O₁₈₄]⁴⁰⁻ by reacting 16 Ag⁺-containing [P₈W₄₈O₁₈₄]⁴⁰⁻ with Ag⁺ using N,N-dimethylformamide (DMF) as a mild reducing agent. This led to a redox-induced structural transformation into a face-centered cubic {Ag₃₀}¹⁶⁺ nanocluster. In this study, we demonstrated the modulation of the electronic states of Ag₃₀ nanoclusters within the ring-shaped POM through two different approaches. A face-centered cubic {Ag₃₀}¹⁸⁺ nanocluster, featuring distinct oxidation states compared to previously reported {Ag₃₀}²²⁺ and {Ag₃₀}¹⁶⁺ nanoclusters, was synthesized using tetra-n-butylammonium borohydride, a stronger reducing agent than DMF, in the reaction of 16 Ag⁺-containing [P₈W₄₈O₁₈₄]⁴⁰⁻ and Ag⁺. Additionally, by leveraging the acid–base properties of POMs, we demonstrated the reversible, stepwise modulation of the charge distribution in the Ag₃₀ nanocluster through controlling protonation states of the ring-shaped POM ligand. These results highlight the potential of engineering POM-stabilized Ag nanoclusters with diverse structures and electronic states, thereby facilitating the exploration of novel properties and applications utilizing the unique characteristics of the POM ligands.

中文翻译：

环形多金属氧酸盐内 Ag30 纳米团簇的电子态调控

原子精确的 Ag 纳米团簇显示出由其结构和电子状态决定的独特特性。然而，操纵 Ag 纳米团簇的电子状态具有挑战性，因为它们具有固有的不稳定性和对不需要的结构变化、分解和聚集的敏感性。最近，我们报道了通过将含 16 Ag⁺ 的 [P₈W₄₈O₁₈₄]⁴⁰⁻ 与 Ag⁺ 反应，合成了封装在环形多金属氧酸盐（POM） [P₈W₄₈O₁₈₄]40− 中的体心立方 {Ag₃₀}²²⁺ 纳米簇使用 N，N-二甲基甲酰胺（DMF）作为温和还原剂。这导致氧化还原诱导的结构转变为面心立方 {Ag₃₀}¹⁶⁺ 纳米团簇。在这项研究中，我们通过两种不同的方法展示了环形 POM 内 Ag₃₀ 纳米团簇的电子态的调制。在含 16 Ag⁺ 的反应中，使用比 DMF 更强的还原剂四正丁基硼氢铵合成了面心立方 {Ag₃₀}¹⁸⁺ 纳米团簇，与先前报道的 {Ag₃₀}²²⁺ 和 {Ag₃₀}¹⁶⁺ 纳米团簇相比，具有不同的氧化态 [P₈W₄₈O₁₈₄]⁴⁰⁻ 和 Ag⁺。此外，通过利用 POM 的酸碱特性，我们证明了通过控制环形 POM 配体的质子化状态来可逆地逐步调节 Ag₃₀ 纳米团簇中的电荷分布。这些结果突出了工程具有不同结构和电子态的 POM 稳定 Ag 纳米团簇的潜力，从而促进了利用 POM 配体的独特特性探索新的特性和应用。

更新日期：2024-09-13

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