MB38(M=Be and Zn): A Quasi‐Planar Structure Rather Than A Core‐Shell Octahedral Borospherene Structure

Abstract In a recent paper (ChemPhysChem, 2023, 24, e202200947), based on the results computed using DFT method, the perfect core‐shell octahedral configuration Be@B 38 and Zn@B 38 was reported to be the global minima of the MB 38 (M=Be and Zn) clusters. However, this paper presents the lower energy structures of MB 38 (M=Be and Zn) clusters as a quasi‐planar configuration, the Be atom is found to reside on the convex surface of the quasi‐planar B 38 isomer, while the Zn atom tends to be attached to the top three B atoms of the quasi‐planar B 38 isomer. Our results show that quasi‐planar MB 38 (M=Be and Zn) at DFT method have lower energy than core‐shell octahedral configuration M@B 38 (M=Be and Zn). Natural atomic charges, valence electron density, electron localization function (ELF) analyses identify the MB 38 (M=Be and Zn) to be charge transfer complexes (Be 2+ B 38 2− and Zn 1+ B 38 1− ) and suggest primarily the electrostatic interactions between doped atom and B 38 fragment. The photoelectron spectra of the corresponding anionic structures were simulated, providing theoretical basis for future structural identification.