Institute for Computational Science and Technology (ICST) , 700000 Ho Chi Minh City , Vietnam.
Department of Chemistry , KU Leuven , B-3001 Leuven , Belgium.
J Phys Chem A. 2019 Sep 26;123(38):8170-8178. doi: 10.1021/acs.jpca.9b04078. Epub 2019 Sep 16.
In the present theoretical study using DFT computations, we successfully designed a series of boron clusters possessing a teetotum shape stabilized upon metal doping. The resulting MB teetotum geometry emerges as a general structural motif for the B boron cluster doped by either two 4 and 5 transition metal atoms. Doping of two different metal atoms also conserves the teetotum motif such as in the mixed RhPdB and IrPtB clusters. A bonding analysis points out that each dimeric metal unit enjoys several stabilizing orbital interactions with an idealized B tubular moiety and thereby establish a bimetallic configuration of [σ(σ-B)] [π(π-B)] [σ(σ-B)] [δ(δ-B)] [σ*(σ-B)] [π*] [σ(σ*-B)] [δ*] for 4d metals and of [σ(σ-B)] [π(π-B)] [σ(σ-B)] [δ(δ-B)] [σ*(σ-B)] [π*] [σ(σ*-B)] [δ*] for 5d metal atoms for 24 electrons. All the MB teetotum structures considered behave as aromatic compounds whose character is indicated by the strongly diatropic current density.
在本使用 DFT 计算的理论研究中，我们成功设计了一系列具有陀螺形状的硼团簇，这些团簇在金属掺杂后得到稳定。所得的 MB 陀螺几何形状是 B 硼团簇被两个 4d 和 5d 过渡金属原子掺杂的通用结构基元。掺杂两个不同的金属原子也可以保持陀螺基元，例如在 RhPdB 和 IrPtB 混合团簇中。成键分析表明，每个二聚金属单元都与理想的 B 管状部分具有几个稳定的轨道相互作用，从而建立了一个双金属构型 [σ(σ-B)] [π(π-B)] [σ(σ-B)] [δ(δ-B)] [σ*(σ-B)] [π*] [σ(σ*-B)] [δ*]对于 4d 金属和 [σ(σ-B)] [π(π-B)] [σ(σ-B)] [δ(δ-B)] [σ*(σ-B)] [π*] [σ(σ*-B)] [δ*]对于 5d 金属原子有 24 个电子。所有考虑的 MB 陀螺结构都表现为芳香化合物，其特征由强烈的反磁电流密度表明。
