Tailoring the Fluorescence of AIE-Active Metal-Organic Frameworks for Aqueous Sensing of Metal Ions.

A hydroxyl-functionalized ligand was designed for the construction of metal-organic framework (MOF) materials with the aggregation-induced emission (AIE) feature, in which the fluorescence can be deliberately tailored: quenching the fluorescence to an "off" state by the decoration with heterocyclic auxiliary ligand 4,4'-bypyridine (Bpy) in the framework as a quenching agent and triggering the enhanced fluorescence to an "on" state by removal of Bpy through the metal competitive coordination substitution strategy. Our study shows that the occurrence of exciton migration between the AIE linker and conjugated auxiliary ligand Bpy causes fluorescence quenching. Time-dependent density functional theory was employed to understand the photoinduced electron transfer process and explain the origins of fluorescence quenching. Using this strategy, the prepared MOF material can perform as a fluorescence "off-on" probe for highly sensitive detection of Al3+ in aqueous media. The hydroxyl group plays a crucial role in sensing as it can selectively chelate Al3+ , which is directly related to the dissociation of nonfluorescent MOF and consequent activation of the AIE process.