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

Abstract

By directly reducing alkynyl-silver precursors, we successfully obtained a large alkynyl-protected silver nanocluster, (C₇ H₁₇ ClN)₃ [Ag₁₁₂ Cl₆ (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 CH₂ Cl₂ 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.