Tri- and Tetra-superatomic Molecules in Ligand-Protected Face-Fused Icosahedral (M@Au 12 ) n (M = Au, Pt, Ir, and Os, and n = 3 and 4) Clusters.

Cluster assembling has been one of the hottest topics in nanochemistry. In certain ligand-protected gold clusters, bi-icosahedral cores assembled from Au 13 superatoms were found to be analogues of diatomic molecules F 2 , N 2 , and singlet O 2 , respectively, in electronic shells, depending upon the super valence bond (SVB) model. However, challenges still remain for extending the scale in cluster assembling via the SVB model. In this work, ligand-protected tri- and tetra-superatomic clusters composed of icosahedral M@Au 12 (M = Au, Pt, Ir, and Os) units are theoretically predicted. These clusters are stable with reasonable highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps and proven to be analogues of simple triatomic (Cl 3 - , OCl 2 , O 3 , and CO 2 ) and tetra-atomic (N≡C-C≡N, and Cl-C≡C-Cl) molecules in both geometric and electronic structures. Moreover, a stable cluster-assembling gold nanowire is predicted following the same rules. This work provides effective electronic rules for cluster assembling on a larger scale and gives references for their experimental synthesis.