Aggregation-Induced Fluorescence-to-Phosphorescence Switching of Molecular Gold Clusters

Aggregation-induced optical responses are ubiquitous among a wide range of organic and inorganic compounds. Here, we demonstrate an unprecedented effect of aggregation on the photoluminescence (PL) profiles of core + exo-type Au84+ clusters, which displayed a change in the dominant PL emission mode from fluorescence to phosphorescence-type upon aggregation. In solvents in which cluster molecules are highly soluble and exist as monomers, they displayed single PL bands at ∼600 nm at ambient temperatures. However, in solvents in which cluster molecules are less soluble and cluster aggregation is induced, a new PL band at ∼700 nm also emerged. Lifetime measurements revealed that the PL emissions at ∼600 and ∼700 nm had fluorescence and phosphorescence characters, respectively. Studies of the excitation spectra suggested that organized cluster assemblies were responsible for the lower-energy emission at ∼700 nm and had exceptionally high emission activity. Accordingly, intense phosphorescence-type emissions were observed in the solid state in which the quantum efficiencies were higher by two orders of magnitude than those of the corresponding monomeric forms in solution. This work provides an example of the critical effects of cluster aggregation events on their optical properties and shows the potential of such effects in the design of cluster-based materials with unique functions and properties.