Zwitterionic Thiolate-Protected Ag22(0/I) and Ag20(I) Clusters: Assembly, Structural Characterization, and Antibacterial Activity
Xin-Yao Wang1,2, Wei Meng3, Hong-Ping Xie1, Dan-Na Song1, Ming-Hao Du1(杜明浩)*, Jin-Xiang Chen3, Pierre Braunstein4, Jian-Ping Lang1,2（郎建平）*
1College of Chemistry, Chemical Engineeringand Materials Science, Soochow University, Suzhou 215123Jiangsu, China
2State Key Laboratory of OrganometallicChemistry, Shanghai Institute of Organic Chemistry, ChineseAcademy of Sciences, Shanghai 200032, China
3Guangdong Provincial Key Laboratory ofNew Drug Screening, Guangzhou Key Laboratory of DrugResearch for Emerging Virus Prevention and Treatment,NMPA Key Laboratory for Research and Evaluation of DrugMetabolism, School of Pharmaceutical Sciences, SouthernMedical University, Guangzhou 510515 Guangdong, China
4Université de Strasbourg - CNRS, Institutde Chimie (UMR 7177 CNRS), 67081 Strasbourg, France
Inorg. Chem. 2024, 63, 13014−13021
Abstract: Zwitterionic thiolate ligands have the potential to introduce novel assembly modes and functions for noble metal clusters. However, their utilization in the synthesis of silver clusters remains understudied, particularly for the clusters containing reductive Ag(0) species. In this article, we report the first synthesis of a mixed-valence silver(0/I) cluster protected by zwitterionic Tab as thiolate ligands (Tab = 4-(trimethylammonio)benzenethiolate), denoted as [Ag22(Tab)24](PF6)20·16CH3OH·6Et2O (Ag22·16CH3OH·6Et2O), alongside an Ag(I) cluster [Ag20(Tab)12(PhCOO)10(MeCN)2(H2O)](PF6)10·11MeCN (Ag20·11MeCN). Ag22 has a distinct hierarchical supratetrahedral structure with a central {Ag6} kernel surrounded by four [Ag4(Tab)6]4+ units. High-resolution electrospray ionization mass spectra demonstrate that Ag22 has two free electrons, indicating a superatomic core. Ag20 has a drum-like [Ag12(Tab)6(PhCOO)6(H2O)]6+ inner core capped by two tetrahedral-like [Ag4(Tab)3(PhCOO)2(MeCN)]2+ units. Ag20 can be transformed into Ag22 after its reaction with NaBH4 in solution. Antibacterial measurements reveal that Ag22 has a significantly lower minimum inhibitory concentration than that of the Ag20 cluster. This work not only extends the stabilization of silver(0/I) clusters to neutral thiol ligands but also offers new materials for the development of novel antibacterial materials.
链接：//pubs.acs.org/doi/10.1021/acs.inorgchem.4c01735
