Re-examining the electronic structure of fluorescent tetra-silver clusters in zeolites

In the present study, we have examined the electronic structures related to the fluorescence properties of small Ag42+ complexes encapsulated in zeolites. We find that interaction between Ag42+ and coordinated water molecules, which was previously proposed to be the origin of fluorescence, may not be a sufficient condition by itself. Refinement of the previously used all-silicon-cage model to include framework Al atoms leads to an asymmetric environment, and this alters the electronic structure in favor of fluorescence. We have further examined the substitution of the H2O ligands by NH3, H2S, PH3, CO and CS. Among these systems, Ag42+ binds most strongly to NH3 but the energetics for the H2S and PH3 complexes is also reasonable. The energy of the fluorescent light is related to the energy of the lowest-energy triplet state, and these energies for the H2O, NH3, H2S and PH3 systems span the range of ∼2-3 eV, i.e., roughly the visible range. Thus, the use of different ligands appears to be an attractive means for tailoring the luminescence properties.