Chiu Tzu-Hao, Pillay Michael N, Wu Ying-Yann, Niihori Yoshiki, Negishi Yuichi, Chen Jie-Ying, Chen Yuan Jang, Kahlal Samia, Saillard Jean-Yves, Liu C W
Department of Chemistry, National Dong Hwa University Hualien 97401 Taiwan Republic of China
Department of Applied Chemistry, Tokyo University of Science 1-3 Kagurazaka, Shinjuku Tokyo 162-8601 Japan.
Chem Sci. 2024 Aug 22;15(36):14660-7. doi: 10.1039/d4sc02920h.
The assembly of discrete superatomic nanoclusters into larger constructs is a significant stride towards developing a new set of artificial/pseudo-elements. Herein, we describe a novel series of 16-electron supermolecules derived from the combination of discrete 8-electron superatomic synthons containing interstitial hydrides as vertex-sharing building blocks. The symmetric (RhH)Ag[SP(OPr)] (1) and asymmetric PtHPtAg[SP(OPr)] (2) are characterized by ESI-MS, SCXRD, NMR, UV-vis absorption spectra, electrochemical and computational methods. Cluster 1 represents the first group 9-doped 16-electron supermolecule, composed of two icosahedral (RhH)@Ag 8-electron superatoms sharing a silver vertex. Cluster 2 results from the assembly of two distinct icosahedral units, Pt@Ag, and (PtH)@Ag. In both cases, the presence of the interstitial hydrides is unprecedented. The stability of the supermolecules is investigated, and 2 spontaneously transforms into PtAg[SP(OPr)] (3) with thermal treatment. The lability of the hydride within the icosahedral framework in solution at low-temperature was confirmed by the VT-NMR.
将离散的超原子纳米团簇组装成更大的结构是朝着开发一系列新型人工/准元素迈出的重要一步。在此，我们描述了一系列新型的16电子超分子，它们由包含间隙氢化物的离散8电子超原子合成子作为顶点共享构建块组合而成。对称的(RhH)Ag[SP(OPr)] (1)和不对称的PtHPtAg[SP(OPr)] (2)通过电喷雾质谱(ESI-MS)、单晶X射线衍射(SCXRD)、核磁共振(NMR)、紫外可见吸收光谱、电化学和计算方法进行了表征。团簇1代表第一个9族掺杂的16电子超分子，由两个共享一个银顶点的二十面体(RhH)@Ag 8电子超原子组成。团簇2由两个不同的二十面体单元Pt@Ag和(PtH)@Ag组装而成。在这两种情况下，间隙氢化物的存在都是前所未有的。对超分子的稳定性进行了研究，并且通过热处理，2自发地转化为PtAg[SP(OPr)] (3)。变温核磁共振(VT-NMR)证实了二十面体框架内的氢化物在低温溶液中的不稳定性。
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