Issue 39, 2024

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

Abstract

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.

Graphical abstract: Electronic state modulation of Ag30 nanoclusters within a ring-shaped polyoxometalate

Supplementary files

Article information

Article type
Paper
Submitted
20 Jun 2024
Accepted
10 Sep 2024
First published
10 Sep 2024

Nanoscale, 2024,16, 18383-18388

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

D. Yanai, K. Yonesato, S. Kikkawa, S. Yamazoe, K. Yamaguchi and K. Suzuki, Nanoscale, 2024, 16, 18383 DOI: 10.1039/D4NR02547D

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