Rh<sub>19</sub><sup>-</sup>: A high-spin super-octahedron cluster.

Jia, Yuhan; Xu, Cong-Qiao; Cui, Chaonan; Geng, Lijun; Zhang, Hanyu; Zhang, Yang-Yang; Lin, Shiquan; Yao, Jiannian et al. · Sci Adv · 2023

basic_science · Level V

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Abstract

Probing atomic clusters with magic numbers is of supreme importance but challenging in cluster science. Pronounced stability of a metal cluster often arises from coincident geometric and electronic shell closures. However, transition metal clusters do not simply abide by this constraint. Here, we report the finding of a magic-number cluster Rh<sub>19</sub><sup>-</sup> with prominent inertness in the sufficient gas-collision reactions. Photoelectron spectroscopy experiments and global-minimum structure search have determined the geometry of Rh<sub>19</sub><sup>-</sup> to be a regular <i>O<sub>h</sub></i>‑[Rh@Rh<sub>12</sub>@Rh<sub>6</sub>]<sup>-</sup> with unusual high-spin electronic configuration. The distinct stability of such a strongly magnetic cluster Rh<sub>19</sub><sup>-</sup> consisting of a nonmagnetic element is fully unveiled on the basis of its unique bonding nature and superatomic states. The 1-nanometer-sized <i>O<sub>h</sub></i>-Rh<sub>19</sub><sup>-</sup> cluster corresponds to a fragment of the face-centered cubic lattice of bulk rhodium but with altered magnetism and electronic property. This cluster features exceptional electron-spin state isomers confirmed in photoelectron spectra and suggests potential applications in atomically precise manufacturing involving spintronics and quantum computing.