σ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−
Document Type
Article
Journal/Book Title
Angewandte Chemie International Edition
Publication Date
6-30-2020
Publisher
Wiley-VCH Verlag GmbH & Co. KGaA
Award Number
NSF, Division of Chemistry (CHE) 1664379
Funder
NSF, Division of Chemistry (CHE)
Volume
59
Issue
39
First Page
17286
Last Page
17290
Abstract
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 ZnMes2 units. 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.
Recommended Citation
H.-L. Xu, I. A. Popov, N. V. Tkachenko, Z.-C. Wang, A. Muñoz-Castro, A. I. Boldyrev, Z.-M. Sun, Angew. Chem. Int. Ed. 2020, 59, 17286.
