Electron counting in cationic and anionic silver clusters doped with a 3d transition-metal atom: endo- vs. exohedral geometry
Electron counting in cationic and anionic silver clusters doped with a 3d transition-metal atom: endo- vs. exohedral geometry
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掺杂 3d 过渡金属原子的阳离子和阴离子银簇中的电子计数：内面几何与外面几何
DOI：
10.1039/d1cp04197e
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发表时间：
2022
影响因子：
3.3
通讯作者：
Terasaki Akira
中科院分区：
文献类型：
--
作者：
Minamikawa Kento;Sarugaku Shun;Arakawa Masashi;Terasaki Akira
电子计数是一个经常支配分子、团簇和复合物性质的概念。在这里，我们探索掺杂过渡金属原子的银团簇，其中三维电子是否离域参与电子计数一直是一个问题。实验是在AgNM+/−(M = Sc-Ni)簇上进行的，通过化学反应性来检查它们的稳定性，通过簇大小、电荷状态和元素周期表上的过渡金属元素来系统地控制价电子的数量。结果表明，除了Cr和Mn掺杂会使3d电子局域化外，18价电子簇中3d电子参与电子计数时，只有在过渡金属原子内腔掺杂时才表现出特殊的稳定性。因此，我们提出了超原子金属团簇的新条目，以及在纳米尺度下调节三维电子行为的几何因子。
Electron counting is a concept that often governs properties of molecules, clusters, and complexes. Here we explore silver clusters doped with a transition-metal atom, where it has been an issue whether or not 3d electrons delocalize to participate in electron counting. The experiment is performed on AgNM+/− (M = Sc–Ni) clusters to examine their stability through chemical reactivity, enabling systematic control of the number of valence electrons by the cluster size, the charge state, and the transition-metal element across the periodic table. It is revealed for 18-valence-electron clusters that 3d electrons participate in electron counting to show exceptional stability only when the transition-metal atom is endohedrally doped, except for Cr and Mn doping that forces 3d electrons to localize. We thus present new entries for superatomic metal clusters as well as a geometric factor that regulates the behavior of 3d electrons in the nanoscale regime.