Yanai Daiki, Yonesato Kentaro, Kikkawa Soichi, Yamazoe Seiji, Yamaguchi Kazuya, Suzuki Kosuke
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, Japan.
Nanoscale. 2024 Oct 10;16(39):18383-18388. doi: 10.1039/d4nr02547d.
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 {Ag} nanocluster encapsulated within a ring-shaped polyoxometalate (POM) [PWO] by reacting 16 Ag-containing [PWO] with Ag using ,-dimethylformamide (DMF) as a mild reducing agent. This led to a redox-induced structural transformation into a face-centered cubic {Ag} nanocluster. In this study, we demonstrated the modulation of the electronic states of Ag nanoclusters within the ring-shaped POM through two different approaches. A face-centered cubic {Ag} nanocluster, featuring distinct oxidation states compared to previously reported {Ag} and {Ag} nanoclusters, was synthesized using tetra--butylammonium borohydride, a stronger reducing agent than DMF, in the reaction of 16 Ag-containing [PWO] and Ag. Additionally, by leveraging the acid-base properties of POMs, we demonstrated the reversible, stepwise modulation of the charge distribution in the Ag 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.
原子精确的银纳米团簇展现出由其结构和电子态所决定的独特性质。然而，由于银纳米团簇固有的不稳定性以及易发生不期望的结构变化、分解和聚集，调控其电子态具有挑战性。最近，我们报道了通过使用N，N-二甲基甲酰胺（DMF）作为温和还原剂，使16个含银的[PWO]与银反应，合成了一种封装在环状多金属氧酸盐（POM）[PWO]内的体心立方{Ag}纳米团簇。这导致了氧化还原诱导的结构转变为面心立方{Ag}纳米团簇。在本研究中，我们通过两种不同方法展示了对环状POM内银纳米团簇电子态的调控。在16个含银的[PWO]与银的反应中，使用比DMF更强的还原剂四丁基硼氢化铵，合成了一种面心立方{Ag}纳米团簇，其具有与先前报道的{Ag}和{Ag}纳米团簇不同的氧化态。此外，通过利用POM的酸碱性质，我们通过控制环状POM配体的质子化状态，展示了银纳米团簇中电荷分布的可逆、逐步调控。这些结果突出了设计具有多样结构和电子态的POM稳定银纳米团簇的潜力，从而有助于利用POM配体的独特特性探索新的性质和应用。
