Turn-On Fluorescence Enantioselective Sensing of Hydroxyl Carboxylic Enantiomers by Metal-Organic Framework Nanosheets with a Homochiral Tetracarboxylate of Cyclohexane Diamide

Two-dimensional (2D) metal-organic frameworks (MOFs) have attracted growing interest due to excellent performance in gas separation, energy conversion and storage, catalysis, and sensing, but their homochirality and exfoliation as well as related enantioselective catalysis and sensing remain a stage of pending exploration owing to the scarcity of homochiral MOFs and intrinsic aggregation of nanosheets. Herein, a homochiral 2D MOF (HMOF-3) with polymeric chirality, good thermostability, and solvent stability is designed and constructed by a homochiral organic ligand 5,5'-((1R,2R)-cyclohexane dicarbonyl bis(azanediyl)) diisophthalic acid (R,R-CHCAIP), a ditopic coligand 4,4'-bipyridine, and Zn salts. Remarkably, HMOF-3 can be exfoliated via solvent-assisted sonication to achieve 2D HMOF-3 nanosheets (HMOF-3-NS), which exhibit a sensitive turn-on effect with the fluorescence enhancement up to 63.5 times in the presence of R/S-mandelic acid, D/L-tartaric acid, D/L-lactic acid, D/L-alanine, and D/L-tryptophan. More importantly, the high surface area, polymeric chirality environment, and highly accessible functional sites on the surface of HMOF-3 nanosheets enable close contact with probed enantiomers, leading to highly enantioselective and sensitive sensing. The turn-on mechanism of host-guestassisted electronic transfer is confirmed by DFT calculation and the relative experiment. This work highlights the promise of homochiral 2D MOF nanosheets for enantioselective sensing applications.

Automated summary

In this study, a homochiral 2D metal-organic framework (HMOF-3) with polymeric chirality was successfully designed and constructed, which could be exfoliated into 2D HMOF-3 nanosheets (HMOF-3-NS). The nanosheets showed promising applications in enantioselective and sensitive sensing, attributed to their high surface area, polymeric chirality environment, and highly accessible functional sites. The turn-on mechanism of host-guest-assisted electronic transfer was confirmed by DFT calculation and experiments, highlighting the potential of homochiral 2D MOF nanosheets for enantioselective sensing applications.