Superatomic Gallium Clusters in Dendrimers: Unique Rigidity and Reactivity Depending on their Atomicity
Superatomic Gallium Clusters in Dendrimers: Unique Rigidity and Reactivity Depending on their Atomicity
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DOI：
10.1002/adma.201907167
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发表时间：
2020-02-21
影响因子：
29.4
通讯作者：
Yamamoto, Kimihisa
中科院分区：
文献类型：
--
作者：
Kambe, Tetsuya;Watanabe, Aiko;Yamamoto, Kimihisa
超原子由于其可能取代其他元素而受到研究。超原子的液相合成是实现超原子可利用性的重要途径。然而，以前的方法基本上仅限于形成单个集群。在这里，研究超原子，并通过设计存在的镓原子的数量来改变这些超原子中的价电子数。基于树枝状分子模板法，已经合成了由3、12、13和其他数目的原子组成的簇。Ga-13的类卤素超原子性质在结构和电化学上被观察到与其他簇完全不同。13和3个原子的镓团簇分别填充2 P和1 P超原子轨道，表现出不同的反应活性。3原子镓团簇被认为是由于未占轨道的能级移动较低而被还原为Ga_3 H_2-。这些镓团簇的结果提供了超原子的候选者。
Superatoms have been investigated due to their possible substitution for other elements. The solution-phase synthesis of superatoms has attracted attention to realize the availability of superatoms. However, the previous approach is basically limited to the formation of a single cluster. Here, superatoms are investigated and the number of valence electrons in these superatoms is changed by designing the number of gallium atoms present. Based on the dendrimer template method, clusters consisting of 3, 12, 13, and other numbers of atoms have been synthesized. The halogen-like superatomic nature of Ga-13 is structurally and electrochemically observed as completely different to the other clusters. The gallium clusters of 13 and 3 atoms, which can fill the 2P and 1P superatomic orbitals, respectively, exhibit different reactivities. The 3-atom gallium cluster is suggested as being reduced to Ga3H2- due to the lower shift of energy levels in the unoccupied orbitals. The results for these gallium clusters provide candidates for superatoms.