MB16− (M=Sc, Y, La): Perfect Bowl‐Like Boron Clusters

Abstract

AbstractThe introduction of transition‐metal doping has engendered a remarkable array of unprecedented boron motifs characterized by distinctive geometries and bonding, particularly those heretofore unobserved in pure boron clusters. In this study, we present a perfect (no defects) boron framework manifesting an inherently high‐symmetry, bowl‐like architecture, denoted as MB16− (M=Sc, Y, La). In MB16−, the B16 is coordinated to M atoms along the C5v‐symmetry axis. The bowl‐shaped MB16− structure is predicted to be the lowest‐energy structure with superior stability, owing to its concentric (2 π+10 π) dual π aromaticity. Notably, the C5v‐symmetry bowl‐like B16− is profoundly stabilized through the doping of an M atom, facilitated by strong d‐pπ interactions between M and boron motifs, in conjunction with additional electrostatic stabilization by an electron transfer from M to the boron motifs. This concerted interplay of covalent and electrostatic interactions between M and bowl‐like B16 renders MB16− a species of exceptional thermodynamic stability, thus making it a viable candidate for gas‐phase experimental detection.