Summary: | Aggregating gold(I) complexes in solution through short aurophilic contacts promotes new photoluminescent deactivation pathways (aggregation-induced emission, AIE). The time dependence of spontaneous AIE is seldom studied. We examine the behavior of complex [Au(<i>N</i><sup>9</sup>-hypoxanthinate)(PTA)] (<b>1</b>) in an aqueous solution with the aid of variable-temperature NMR, time-resolved UV–Vis and photoluminescence spectroscopy, and PGSE NMR. The studies suggest that partial ligand scrambling in favor of the ionic [Au(PTA)<sub>2</sub>][Au(<i>N</i><sup>9</sup>-hypoxanthinate)<sub>2</sub>] pair followed by anion oligomerization takes place. The results are rationalized with the aid of computational calculations at the TD-DFT level of theory and IRI analysis of the electron density.
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