Controlling the Nature of Photoluminescence of Emissive Metal Nanoclusters

Abstract Photoluminescence (PL) serves as one of the most attractive chemical‐physical properties of metal nanoclusters. However, the control over the PL nature of metal nanoclusters as fluorescence or phosphorescence remains challenging. Basically, the PL nature control concerns the transition regulation of excited electrons in nanoclusters from their excited state to the ground state. Up to the present, some cases have been reported on adjusting the PL nature of emissive nanoclusters via different means, including the composition regulation, the isomerization, the aggregation, and the temperature variation. At the same time, theoretical calculations have been performed to thoroughly understand the PL nature transformation of these emissive nanoclusters in terms of their electronic structures and transition pathways. This Concept highlights and reviews the recent progress in controlling the PL nature of emissive nanoclusters as fluorescence or phosphorescence, which hopefully paves the way for fabricating novel nanoclusters or cluster‐based nanomaterials with customized PL properties.