The 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 (2π+10π) 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.

中文翻译：

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MB16 - (M = Sc, Y, La)：完美的碗状硼团簇

过渡金属掺杂的引入产生了一系列前所未有的硼图案，其特征是独特的几何形状和键合，特别是迄今为止在纯硼簇中未观察到的硼图案。在这项研究中，我们提出了一个完美（无缺陷）的硼框架，表现出固有的高对称性、碗状结构，表示为MB16−（M = Sc，Y，La）。在MB16−中，B16沿着C5v对称轴与M原子配位。由于其同心（2π+10π）双π芳香性，碗形MB16−结构被预测为具有优异稳定性的最低能量结构。值得注意的是，C5v 对称碗状 B16− 通过 M 原子的掺杂而得到高度稳定，M 和硼基序之间的强 d-pπ 相互作用促进了这一点，同时通过从 M 到硼的电子转移实现了额外的静电稳定。主题。 M 和碗状 B16 之间的共价和静电相互作用的协同相互作用使 MB16− 具有出色的热力学稳定性，从而使其成为气相实验检测的可行候选者。