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σ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−

dc.contributor.authorXu H.-L.
dc.contributor.authorPopov I.A.
dc.contributor.authorTkachenko N.V.
dc.contributor.authorWang Z.-C.
dc.contributor.authorMuñoz-Castro A.
dc.contributor.authorBoldyrev A.I.
dc.contributor.authorSun Z.-M.
dc.date.accessioned2020-09-02T22:30:34Z
dc.date.available2020-09-02T22:30:34Z
dc.date.issued2020
dc.identifier10.1002/ange.202008276
dc.identifier.issn00448249
dc.identifier.urihttps://hdl.handle.net/20.500.12728/6636
dc.descriptionIn 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. © 2020 Wiley-VCH GmbH
dc.language.isoen
dc.publisherWiley-Blackwell
dc.subjectplanar tetracoordinate Zn/Cd
dc.subjectsupertetrahedron
dc.subjectTd symmetry
dc.subjectZintl clusters
dc.subjectσ-aromaticity
dc.titleσ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−
dc.typeArticle


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