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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.
This work was supported by the National Science Fund for Distinguished Young Scholars (No. 21825106), the National Natural Science Foundation of China (Nos. 21975065 and 21671175), the Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 164100510005), and the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province (No. 19IRTSTHN022) and Zhengzhou University.