Rod-Shaped Silver Supercluster Unveiling Strong Electron Coupling between Substituent Icosahedral Units

The first linear silver supercluster based on icosahedral Ag13 units has been constructed via bridging of dpa ligands: Ag61(dpa)27(SbF6)4 (Hdpa = dipyridylamine) (Ag61). Single-crystal X-ray diffraction reveals that this rod-shaped cluster consists of four vertex-sharing Ag13 icosahedra in a linear arrangement. This Ag61 cluster represents the longest one-dimensional metal nanocluster with a resolved structure. Unprecedented electron coupling develops between their constituent Ag13 units. Theoretical studies disclose that the stabilities of the two superclusters are dictated by a strong interaction between the Ag13 units as well as the ligand effect of the dpa-Ag motifs. The quantum size effect accounts for the significant enhancement of the metal-related absorptions and the red shift at the near-infrared region as the length of the cluster increases. This work sheds light on the evolution of one-dimensional materials and an understanding of the electronic communication between the constituent clusters.