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

In a recent paper (ChemPhysChem, 2023, 24, e202200947), based on the results computed using DFT method, the perfect core-shell octahedral configuration Be@B₃₈ and Zn@B₃₈ was reported to be the global minima of the MB₃₈(M=Be and Zn) clusters. However, this paper presents the lower energy structures of MB₃₈(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 B₃₈ isomer, while the Zn atom tends to be attached to the top three B atoms of the quasi-planar B₃₈ isomer. Our results show that quasi-planar MB₃₈(M=Be and Zn) at DFT method have lower energy than core-shell octahedral configuration M@B₃₈(M=Be and Zn). Natural atomic charges, valence electron density, electron localization function (ELF) analyses identify the MB₃₈(M=Be and Zn) to be charge transfer complexes (Be²⁺B₃₈ ^2-and Zn¹⁺B₃₈ ^1-) and suggest primarily the electrostatic interactions between doped atom and B₃₈ fragment. The photoelectron spectra of the corresponding anionic structures were simulated, providing theoretical basis for future structural identification.