Spherical Aromaticity of All‐Metal [Bi@In 8 Bi 12 ] 3−/5− Clusters

Tkachenko, Nikolay V.  (ORCID:0000000272964293); Zhang, Xiang‐Wen; Qiao, Lei; Shu, Cong‐Cong; Steglenko, Dmitry  (ORCID:0000000287936789); Muñoz‐Castro, Alvaro  (ORCID:0000000159499449); Sun, Zhong‐Ming  (ORCID:0000000328946327); Boldyrev, Alexander I.  (ORCID:0000000282773669)

doi:10.1002/chem.201905264

The reactivity of Bi_n⁻clusters (n= 2 to 30) with O₂is found to display even-odd alternations. The open-shell even-sized Bi_n⁻clusters are more reactive than the closed-shell odd-sized clusters, except Bi₁₈⁻, which exhibits no observable reactivity toward O₂. We have investigated the structure and bonding of Bi₁₈⁻to understand its remarkable resistance to oxidation. We find that the most stable structure of Bi₁₈⁻consists of two Bi₈cages linked by a Bi₂dimer, where each atom is bonded to three neighboring atoms. Chemical bonding analyses reveal that each Bi uses its three 6pelectrons to form three covalent bonds with its neighbors, resulting in a Bi₁₈⁻cluster without any dangling bonds. We find that the robust Bi₁₈framework along with the totally delocalized unpaired electron is responsible for the surprising inertness of Bi₁₈⁻toward O₂. The Bi₁₈framework is similar to that in Hittorf’s phosphorus, suggesting the possibility to create bismuth nanoclusters with interesting structures and properties.

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