Abstract
The properties of metal nanoclusters depend on both their structures and electronic states. However, in contrast to the significant advances achieved in the synthesis of structurally well-defined metal nanoclusters, systematic control of their electronic states is still challenging. In particular, stimuli-responsive and reversible control of the electronic states of metal nanoclusters is attractive from the viewpoint of their practical applications. Recently, we developed a synthesis method for atomically precise Ag nanoclusters using polyoxometalates (POMs) as inorganic ligands. Herein, we exploited the acid/base nature of POMs to reversibly change the electronic states of an atomically precise {Ag(27)} nanocluster via protonation/deprotonation of the surrounding POM ligands. We succeeded in systematically controlling the electronic states of the {Ag(27)} nanocluster by adding an acid or a base (0-6 equivalents), which was accompanied by drastic changes in the ultraviolet-visible absorption spectra of the nanocluster solutions. These results demonstrate the great potential of Ag nanoclusters for unprecedented applications in various fields such as sensing, biolabeling, electronics, and catalysis.