High photoluminescence from self-assembled Ag₂Cl₂(dppe)₂ clusters through metallophilic interactions

Ligand protected metal nanoclusters (NCs) are an emerging class of functional materials with intriguing photophysical and chemical properties. The size and molecular structure play an important role in endowing NCs with characteristic optical and electronic properties. Modulation of these properties through the chemical reactivity of NCs is largely unexplored. Here, we report on the synthesis of self-assembled Ag₂Cl₂(dppe)₂ clusters through the ligand-exchange-induced transformation of [Pt₂Ag₂₃Cl₇(PPh₃)₁₀] NCs [(dppe): 1,2-bis(diphenylphosphino)ethane; (PPh₃): triphenylphosphine]. The single crystal x-ray structure reveals that two Ag atoms are bridged by one dppe and two Cl ligands, forming a Ag₂Cl₂(dppe) cluster, which is subsequently self-assembled through dppe ligands to form [Ag₂Cl₂(dppe)₂]_n. Importantly, the Ag₂Cl₂(dppe)₂ cluster assembly exhibits high photoluminescence quantum yield: ∼18%, which is attributed to the metallophilic interactions and rigidification of the ligand shell. We hope that this work will motivate the exploitation of the chemical reactivity of NCs as a new path to attain cluster assemblies endowed with enhanced photophysical properties.