Construction of Silver Clusters Capped by Zwitterionic Ethynide Ligands

• Published in: Inorganic chemistry 2021-05, Vol.60 (9), p.6276-6282
• Main Authors: Shen, Yang-Lin, Jin, Jun-Ling, Fang, Jun-Jie, Liu, Zheng, Shi, Jian-Lin, Xie, Yun-Peng, Lu, Xing
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.0c03790

A zwitterionic ligand 3-(triethylammonio)­propyne (TAP) has been employed to construct nine silver ethynide compounds for the first time. Single-crystal X-ray analyses reveal that compounds 1 and 2 are silver ethynide assemblies based on the Ag3 subunits and clusters 3–8 are small discrete clusters of Ag3, Ag6, Ag8, and Ag12, respectively, ligated by the bulky TAP ligand with different auxiliary ligands. In addition, upon acquiring the tripod-like t BuPO3 2–, a unprecedented 80 nuclei silver ethynide cluster was isolated and determined to be [(CF3CO2)5@Ag80(TAP)14( t BuPO3)16(CF3CO2)24]19+ by crystallography and thermogravimetric analysis. The C 1 symmetry of Ag80 was deconstructed to be two [Ag40(TAP)7( t BuPO3)8(CF3CO2)12]12+ secondary building subunits arranged in a cross way, with five CF3CO2 – trapped in the center. These results highlight that the elaborate selection of ethynide ligands is of great importance in the synthesis of novel silver ethynide clusters.