σ‐Aromaticity‐Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn 6 Ge 16 ] 4− and [Cd 6 Ge 16 ] 4−
σ‐Aromaticity‐Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn 6 Ge 16 ] 4− and [Cd 6 Ge 16 ] 4−
复制标题
- 芳香性 - 异金属超四面体团簇 [Zn 6 Ge 16 ] 4 - 和 [Cd 6 Ge 16 ] 4 - 的诱导稳定性
DOI：
10.1002/anie.202008276
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Sun, Zhong‐Ming
中科院分区：
文献类型：
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作者：
Xu, Hong‐Lei;Popov, Ivan A.;Tkachenko, Nikolay V.;Wang, Zi‐Chuan;Muñoz‐Castro, Alvaro;Boldyrev, Alexander I.;Sun, Zhong‐Ming
在这项工作中，最大的异金属超四面体团簇[Zn 6 Ge 16]4−和[Cd 6 Ge 16]4−通过高电荷的[Ge 4]4−单元和过渡金属阳离子直接自组装，其中Ge 2 Zn或Ge 2Cd三角形中的3中心2电子σ键对整个结构的稳定起着至关重要的作用。团簇结构具有一个开放的框架与一个大的中心空腔的直径为4.6毫米的锌和5.0毫米的镉，分别。 随时间变化的HRESI-MS谱表明，较大的团簇由具有单个[Ge 4]4−和ZnMes 2单元的较小组分生长而成。在DFT水平上进行的计算表明，[M6 Ge 16]4−（2.22 eV）中有非常大的HOMO-LUMO能隙，这表明高动力学稳定性可能为材料科学提供机会。 这些发现为高对称性的异金属团簇的组装提供了一种新的策略。
In this work, the largest heterometallic supertetrahedral clusters, [Zn6Ge16]4−and [Cd6Ge16]4−, were directly self‐assembled through highly‐charged [Ge4]4−units and transition metal cations, in which 3‐center–2‐electron σ bonding in Ge2Zn or Ge2Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time‐dependent HRESI‐MS spectra show that the larger clusters grow from smaller components with a single [Ge4]4−and ZnMes2units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M6Ge16]4−(2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry.