Zeolite confined silver clusters (AgCLs) have attracted extensive attention due to their remarkable luminescent properties, but the elucidation of the underlying photophysical processes and especially the excited-state dynamics remains a challenge. Herein, we investigate the bright photoluminescence of AgCLs confined in Linde Type A zeolites (LTA) by systematically varying the temperature (298-77 K) and co-cation composition (Li/Na) and examining their respective influence on the steady-state and time-resolved photoluminescence. The observed polychromatic emission of the tetrahedral Ag4(H2O) n 2+ clusters ranges from orange to violet and three distinct emitting species are identified, corresponding to three long-lived triplet states populated consecutively and separated by a small energy barrier. These long-lived species are at the origin of the polychromatic luminescence with high photoluminescence quantum yields. Furthermore, the Li-content dependence of decay times points to the importance of guest-host-guest interactions in tuning the luminescent properties with a 43% decrease of the dominating decay time by increasing Li content. Based on our findings, a simplified model for the photophysical kinetics is proposed that identifies the excited-state processes. The results outlined here pave the way for a rational design of confined metal clusters in various frames and inspire the specified applications of Ag-zeolites.
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