A facile synthesis of highly stable and luminescent Ag clusters: a steady-state and time-resolved spectroscopy study

In this paper, we reported a very simple and environmentally friendly procedure for the synthesis of bright luminescent and nearly monodisperse Ag nanoclusters stabilized by a poly(N-vinylpyrrolidone) homopolymer. In this synthesis route acetonitrile or N,N-dimethylformamide (DMF) acts as both solvent and a reducing agent at their respective reflux temperatures. The as-prepared Ag clusters were found to be highly stable in various solvents as well as show nearly no changes in their emission intensity in solutions with different pH values and ionic strengths. Remarkably, the acetonitrile method predominantly produces blue emitting Ag clusters with a photoluminescence (PL) emission maximum at 424 nm (quantum yield 3.5%), whereas mainly blue-green emitting Ag clusters with the PL emission maximum at 450 nm (quantum yield 2.7%) were formed using the DMF method. The photo-physical, electronic, structural and morphological properties of the Ag clusters were investigated by performing UV/Vis absorption spectroscopy, stationary and time-resolved PL spectroscopy, X-ray photoelectron spectroscopy, femtosecond transient absorption spectroscopy, and transmission electron microscopy experiments.