Evolution of all-carboxylate-protected superatomic Ag clusters confined in Ti-organic cages
Xi‐Ming Luo, Chunhua Gong, Xi‐Yan Dong, Lei Zhang, Shuang‐Quan Zang
Abstract
In this study, the size of the titanium organic cage was controlled to achieve the restricted growth from a single Ag(I) atom (Ag@Ti5) to rare all-carboxylate-protected superatomic Ag cluster (Ag6@Ti6). The classical octahedral Ag64+ cluster with two delocalized electrons (2e) has been encapsulated in a Ti6 organic cage, which shows high stability in air and dimethyformamide (DMF). Furthermore, larger 2e nested double-tetrahedra Ag clusters (Ag86+ and Ag97+) protected using a tetrahedral hollow metalloligand framework (Ag8@Ti4 and Ag9@Ti4) were obtained. Electrospray ionization mass spectrometry (ESI-MS) and density functional theory (DFT) calculations confirmed that there are two delocalized electrons on these small Ag clusters. This study provides a new form of protection for superatomic Ag clusters and provides a feasible strategy for the development of stable Ag clusters.