4.7 Article

On Close Parallels between the Zintl-Based Superatom Ge9Be and Chalcogen Elements

Journal

INORGANIC CHEMISTRY
Volume 60, Issue 5, Pages 3196-3206

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c03531

Keywords

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Funding

  1. National Natural Science Foundation of China [21573089, 51872057]
  2. 13th Five-Year Plan Science and Technology Research Project of Jilin Provincial Education Department [JJKH20190117KJ]
  3. Graduate Innovation Fund of Jilin University [101832018C108, 101832020CX111]
  4. Training Program for the Distinguished Young Scholar in the University of Fujian Province [2018B032]

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The Zintl cluster Ge9Be has been identified as a potential member of the superatom family due to its similarity to chalcogen elements. It has the ability to form stable ionic compounds and covalent compounds with multiple valence superatoms. Utilizing solid Zintl clusters, stable superatom motifs can be designed and synthesized for specific characteristics-oriented applications.
Ever since the concept of superatoms was brought forward in the 1990s, various specific types of clusters have been proposed to mimic atomic properties and enrich the threedimensional periodic table. In this work, a Zintl cluster, namely, Ge9Be, has been certified eligible to join the superatom family, owing to its surprising similarity to chalcogen elements. Having 38 valence electrons, Ge9Be has an intrinsic desire to gain two additional electrons to achieve electronic shell closure, in which its quasi-chalcogen identity roots. Like oxygen-group elements, Ge9Be has the potential to form stable ionic compounds with lithium, beryllium, calcium, and superalkaline-earth atom FLi3. On the other hand, the combination of Ge 9 Be and the multiple valence superatom Al-7(-) results in covalent compounds resembling carbon oxides. Close parallels have also been found between (Ge9Be)(2)-based compounds and common peroxides, further evidencing the superatom characteristics of Ge9Be. This finding puts forward an almost perfect superatom counterpart of group VIA elements and opens the door to characteristics-oriented design and synthesis of stable superatom motifs by utilizing solid Zintl clusters.

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