Ca@Pb<sub>12</sub>: A Viable All-Main-Group-Metal Endofullerene That Imitates the Transition Metals
Herein, we report the Ca@Pb<sub>12</sub> cluster, an all-main-group-metal endofullerene possessing the highly symmetric icosahedral (<i>I</i><sub><i>h</i></sub>) Platonic solid structure. The endohedral environment endows the Ca atom with concrete transition-metal-like bonding behaviors, as evidenced by the 18e (in 3d<sup>10</sup>4s<sup>2</sup>4p<sup>6</sup> configuration) valence shell structure and five strong Pb<sub>12</sub> → Ca(3d) dative bonds, whose orbital interaction energy (Δ<i>E</i><sub>orb</sub>, -134.2 kcal/mol) represents 54.9% of total Δ<i>E</i><sub>orb</sub> (-244.4 kcal/mol) between Ca<sup>2+</sup> and [Pb<sub>12</sub>]<sup>2-</sup>. Moreover, since the favorable orbital interactions can compensate for the enlarged steric repulsion during encapsulation, Ca@Pb<sub>12</sub> is thermodynamically stable, dynamically rigid (up to 1300 K), and electronically robust, as verified by large HOMO-LUMO gaps (4.58 eV), high vertical detachment energy (6.39 eV), and low electron affinity (-0.71 eV). It is the first viable all-main-group-metal endofullerene, where the guest alkaline earth metal exhibits the typical bonding behaviors of transition metals.
Authors
- Bin Huo (ORCID: https://orcid.org/0000-0002-3242-9026)
- Yan‐Bo Wu (ORCID: https://orcid.org/0000-0001-6032-9957)
- Xiao‐Ling Guan (ORCID: https://orcid.org/0009-0005-8235-5212)
- Caixia Yuan (ORCID: https://orcid.org/0000-0002-3681-4423)
Institutions
- Shanxi University of Traditional Chinese Medicine (CN)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-02-07
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c05250
- Citations
- 3
- Primary Topic
- Fullerene Chemistry and Applications
- Type
- article
- Field-Weighted Citation Impact
- 2.81
Funders
- National Natural Science Foundation of China
- Natural Science Foundation of Shanxi Province