Superatomic Gallium Clusters in Dendrimers: Unique Rigidity and Reactivity Depending on their Atomicity

Abstract 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 Ga₁₃ 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.