Unusual structural transformation and luminescence response of magic-size silver(I) chalcogenide clusters ligand-exchange.

Structural transformations of nanoclusters provide a platform to tune their properties and understand the fundamental science due to their intimate structure-property correlation. Here, we present an alkynyl ligand-exchange induced growth of atomically precise silver(I) clusters, which are particularly of interest because of their luminescence response at room temperature. SCXRD and UV-vis map out the growth steps of the cluster from [AgS(CCBu)] featuring a pseudo- concave AgS to [AgS(CCPhBr)] with a pseudo- core-shell AgS@Ag@Ag, which is driven by a thermodynamic route under the disruption of ligands. To our knowledge, the findings in this work establish the first example of ligand-exchange as a versatile tool for tuning the size and luminescence of semiconductor silver(I) clusters.