Raising Near-Infrared Photoluminescence Quantum Yield of Au₄₂ Quantum Rod to 50% in Solutions and 75% in Films

Highly emissive gold nanoclusters (NCs) in the near-infrared (NIR) region are of wide interest, but challenges arise from the excessive nonradiative dissipation. Here, we demonstrate an effective suppression of the motions of surface motifs on the Au₄₂(PET)₃₂ rod (PET = 2-phenylethanethiolate) by noncoordinative interactions with amide molecules and accordingly raise the NIR emission (875/1045 nm peaks) quantum yield (QY) from 18% to 50% in deaerated solution at room temperature, which is rare in Au NCs. Cryogenic photoluminescence measurements indicate that amide molecules effectively suppress the vibrations associated with the Au-S staple motifs on Au₄₂ and also enhance the radiative relaxation, both of which lead to stronger emission. When Au₄₂ NCs are embedded in a polystyrene film containing amide molecules, the PLQY is further boosted to 75%. This research not only produces a highly emissive material but also provides crucial insights for the rational design of NIR emitters and advances the potential of atomically precise Au NCs for diverse applications.