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.
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NSF, Division of Chemistry (CHE)
Utah State University
NSF, Division of Chemistry (CHE) 1664379
Deciphering Delocalized Bonding in Excited States, Solvated Species and Novel 0-, 1-, 2-, and 3-Dimensional Chemical Systems
See README.txt file.
Xu, H., Popov, I. A., Tkachenko, N. V., Wang, Z., Muñoz‐Castro, A., Boldyrev, A. I., & Sun, Z. (2020). σ‐Aromaticity‐Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn 6 Ge 16 ] 4− and [Cd 6 Ge 16 ] 4−. Angewandte Chemie, 132(39), 17439–17443. https://doi.org/10.1002/ange.202008276
This work is licensed under a Creative Commons Attribution 4.0 License.
Boldyrev, A. I., & Tkachenko, N. (2021). Data from: σ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−. Utah State University. https://doi.org/10.26078/N8GJ-1G18
Additional FilesREADME.txt (2 kB)
Chemical_Bonding_of_[Cd6Ge16]4-.zip (26177 kB)
Chemical_Bonding_of_[Zn6Ge16]4-.zip (34618 kB)
Supporting_Information.pdf (2216 kB)