A 34‐Electron Superatom Ag₇₈ Cluster with Regioselective Ternary Ligands Shells and Its 2D Rhombic Superlattice Assembly

Herein, we report a 78‐nuclei silver nanocluster (NC) [Ag 78 ( i PrPhS) 30 (dppm) 10 Cl 10 ] 4+ ( SD/Ag78a ; dppm=bis‐(diphenylphosphino)methane) that was synthesized through a one‐pot reaction using [Ag(pz)] n as precursor (Hpz=pyrazole) and further characterized by X‐ray crystallography. SD/Ag78a shows a core–shell structure comprised of an all‐metallic Ag 53 kernel surrounded by an Ag 25 discontinuous metal–organic shell. The Ag 53 kernel is an Ag 13 Ino decahedron encaged by an Ag 40 drum‐like shell, while the Ag 25 shell consists of two Ag 10 S 10 P 10 Cl 5 rings and five S‐Ag‐S staples. Three types of ligands regioselectively cap on the surface of the Ag 78 NC, forming diverse metal–ligand interfacial structures. The NC is a closed‐shell 34‐electron superatom with +4 charge state and shows highly featured molecule‐like absorption spectra in the UV/Vis region with a maximum around 493 nm. The rhombic superlattice assembled from SD/Ag78a through intercluster C−H⋅⋅⋅π interactions can be formed by a simple drop‐casting treatment.