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

• Published in: Journal of the American Chemical Society Vol. 143; no. 31; pp. 12261 - 12267
• Main Authors: Yuan, Shang-Fu, Xu, Cong-Qiao, Liu, Wen-Di, Zhang, Jing-Xuan, Li, Jun, Wang, Quan-Ming
• Format: Journal Article
• Language: English
• Published: American Chemical Society 11.08.2021
• Subjects: ligands; silver; X-ray diffraction
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.1c05283

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) (Ag 61 ). Single-crystal X-ray diffraction reveals that this rod-shaped cluster consists of four vertex-sharing Ag13 icosahedra in a linear arrangement. This Ag 61 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.