A small bimetallic Ag₃Cu₂ nanocluster with dual emissions within and against Kasha's rule

Single crystals of a small bimetallic Ag₃Cu₂ nanocluster protected by six ligands of 2,4-dimethylbenzene thiol are synthesized by a one-pot procedure of wet chemistry. This Ag₃Cu₂ nanocluster bears a trigonal bipyramid metallic core with two copper atoms located on both sides of a triangular Ag₃. Interestingly, the six Cu-Ag side edges of the trigonal bipyramid are fully protected by the six ligands giving rise to reinforced stability and high chemical purity. More interestingly, this Ag₃Cu₂ cluster shows strong dual fluorescence emissions in both ultraviolet visible (UV-vis) and near infrared (NIR) regions. Theoretical calculations reproduce the absorption and fluorescence spectra where the NIR emission at 824 nm is assigned to the S₁→ S₀ transition, while the simultaneous emission in the visible band is due to the radiation of highly excited states and is against Kasha's rule.