Formation of an Alkynyl‐Protected Ag112 Silver Nanocluster as Promoted by Chloride Released In Situ from CH2Cl2

• Published in: Angewandte Chemie International Edition Vol. 59; no. 13; pp. 5312 - 5315
• Main Authors: Hu, Feng, Li, Jiao‐Jiao, Guan, Zong‐Jie, Yuan, Shang‐Fu, Wang, Quan‐Ming
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 23.03.2020
• Edition: International ed. in English
• Subjects: alkynyl ligands; Chloride ions; chloride ligands; cluster compounds; Core-shell structure; Dichloromethane; Mass spectrometry; Mass spectroscopy; Nanoclusters; optical properties; silver
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201915168

By directly reducing alkynyl–silver precursors, we successfully obtained a large alkynyl‐protected silver nanocluster, (C7H17ClN)3[Ag112Cl6(C≡CAr)51], which is hitherto the largest structurally characterized silver nanocluster in the alkynyl family. The cluster exhibits four concentric core–shell structures (Ag13@Ag42@Ag48@Ag9), and four types of alkynyl–silver binding modes are observed. Chloride was found to be critical for the stabilization and formation of the silver nanocluster. The release of chloride ions in situ from CH2Cl2 solvent has been confirmed by mass spectrometry. This study suggests that the combination of alkynyl and halide ligands will pave a new way for the synthesis of large silver nanoclusters. Clever Cl: A large silver nanocluster, [Ag112Cl6(C≡CAr)51]3−, composed of four concentric core–shell structures (Ag13@Ag42@Ag48@Ag9) was obtained by reducing alkynyl–silver precursors with the weak reducing agent diphenylsilane. The in situ release of chloride ions from the CH2Cl2 solvent was critical for formation of the nanocluster, in which four different alkynyl–silver binding modes are observed (see picture).