Yonesato Kentaro, Yamazoe Seiji, Kikkawa Soichi, Yokogawa Daisuke, 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.
Chem Sci. 2022 Apr 12;13(19):5557-5561. doi: 10.1039/d2sc01156e. eCollection 2022 May 18.
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} nanocluster protonation/deprotonation of the surrounding POM ligands. We succeeded in systematically controlling the electronic states of the {Ag} 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.
金属纳米团簇的性质取决于其结构和电子态。然而，与在合成结构明确的金属纳米团簇方面取得的重大进展形成对比的是，对其电子态进行系统控制仍然具有挑战性。特别是，从实际应用的角度来看，对金属纳米团簇的电子态进行刺激响应性和可逆控制很有吸引力。最近，我们开发了一种使用多金属氧酸盐（POMs）作为无机配体来合成原子精确的银纳米团簇的方法。在此，我们利用POMs的酸碱性质，通过周围POM配体的质子化/去质子化来可逆地改变原子精确的{Ag}纳米团簇的电子态。我们通过添加酸或碱（0 - 6当量）成功地系统控制了{Ag}纳米团簇的电子态，这伴随着纳米团簇溶液紫外可见吸收光谱的剧烈变化。这些结果证明了银纳米团簇在传感、生物标记、电子学和催化等各个领域实现前所未有的应用的巨大潜力。
