Unique Fluorescence Turn-On and Turn-Off-On Responses to Acids by a Carbazole-Based Metal-Organic Framework and Theoretical Studies

Distinct from predominately known fluorescence quenching (turn-off) detection, turn-on response to hazardous substances by luminescent metal-organic frameworks (LMOFs) could greatly avoid signal loss and susceptibility to environmental stimulus. However, such detection rarely occurs and lacks theoretical elucidations. Here, we present the first example of unique turn-on and unprecedented turn-off-on responses to a variety of acids by a stable 12-connected hexanuclear Y(III)-cluster-based LMOF material-JLU-MOF111, featuring the nondefault pcu topology. Benefiting from the "pocket" structures formed by the carbazole-containing ligands, JLU-MOF111 can sense multiple inorganic and organic acids via different degrees of fluorescence turn-on behaviors. Particularly, turn-on sensing of HNO3, HCl, HBr, and TFA is hypersensitive with LODs as low as the ppb level. Theoretical calculations confirm weak interactions in acid-ligand complexes, which lead to constrained rotations of benzene moieties of the ligands when the complexes decay from excited states. These account for the turn-on response through reduced nonradiative energy consumption that competes with emissive decay. The turn-off-on response to 4-NBA and 3,5-DNBA involves an excited-state electron transfer process that dominates the turn-off stage and prohibited nonradiative decay that competes with the intrinsic emission of the ligand and dominates the turn-on stage. This work has a guiding significance for the full-scale understanding of turn-on and turn-off-on sensing performance in LMOF materials and beyond.