Probing the Nature of the Transition-Metal-Boron Bonds and Novel Aromaticity in Small Metal-Doped Boron Clusters Using Photoelectron Spectroscopy.

Photoelectron spectroscopy combined with quantum chemistry has been a powerful approach to elucidate the structures and bonding of size-selected boron clusters (B_n^-), revealing a prevalent planar world that laid the foundation for borophenes. Investigations of metal-doped boron clusters not only lead to novel structures but also provide important information about the metal-boron bonds that are critical to understanding the properties of boride materials. The current review focuses on recent advances in transition-metal-doped boron clusters, including the discoveries of metal-boron multiple bonds and metal-doped novel aromatic boron clusters. The study of the RhB^- and RhB₂O^- clusters led to the discovery of the first quadruple bond between boron and a transition-metal atom, whereas a metal-boron triplebond was found in ReB₂O^- and IrB₂O^-. The ReB₄^- cluster was shown to be the first metallaborocycle with Möbius aromaticity, and the planar ReB₆^- cluster was found to exhibit aromaticity analogous to metallabenzenes.