Solvent Polarity-Dependent Behavior of Aliphatic Thiols and Amines toward Intriguingly Fluorescent AuAgGSH Assembly

Highly stable fluorescent glutathione (GSH)-protected AuAg assembly has been synthesized in water under UV irradiation. The assembly is composed of small Ag₂/Ag₃ clusters. These clusters gain stability through synergistic interaction with Au­(I) present within the assembly. This makes the overall assembly fluorescent. Here, GSH acts as a reducing as well as stabilizing agent. The assembly is so robust that it can be vacuum-dried to solid particles. The as-obtained solid is dispersible in nonaqueous solvents. The interaction between solvent and the assembly provides stability to the assembly, and the assembly shows fluorescence. It is interesting to see that the behavior of long-chain aliphatic thiols or amines toward the fluorescent assembly is altogether a different phenomenon in aqueous and nonaqueous mediums. The assembly gets ruptured in water due to direct interaction with long-chain thiols or amines, whereas in nonaqueous medium, solvation of added thiols or amines becomes pronounced, which hinders the interaction of solvent with the assembly. However, the fluorescence of the assembly is always quenched with thiols or amines no matter what the solvent medium is. In aqueous medium, the fluorescence quenching by aliphatic thiol or amine becomes pronounced with successive decrease in their chain length, whereas in nonaqueous medium, the trend is just reversed with chain length. The reasons behind such an interesting reversal of fluorescence quenching in aqueous and nonaqueous solvents have been discussed explicitly. Again, in organic solvents, thiol or amine-induced quenched fluorescence is selectively recovered by Pb­(II) ion without any alteration of excitation and emission maxima. This phenomenon is not observed in water because of the ruptured fluorescent assembly. The fluorescence recovery by Pb­(II) and unaltered emission peak only in nonaqueous solvent unequivocally prove the engagement of Pb­(II) with thiols or amines, which in turn revert the original solvent-supported stabilization of the assembly.