Abstract
Luminescent chiral metal-organic frameworks (CMOFs) are promising candidates for the enantioselective sensing of important chiral molecules. Herein, we report the synthesis and characterization of Zn and Cd CMOFs based on 1,1'-bi-2-naphthol (BINOL)-derived 3,3',6,6'-tetra(benzoic acids), H4L-OEt and H4L-OH. Four CMOFs, Zn-L-OEt, Zn-L-OH, Cd-L-OEt, and Cd-L-OH, based on these ligands were crystallographically characterized. Zinc cations form 8-connected (8-c) penta-metallic secondary building units (SBUs), while cadmium cations form 4-c trimetallic SBUs. These SBUs are linked by 4-c L-OEt and L-OH ligands to form noninterpenetrated 4, 8-c 4,8T41 zinc CMOFs (Zn-L-OEt and Zn-L-OH) and 2-fold interpenetrated 4-c diamondoid (dia) cadmium CMOFs (Cd-L-OEt and Cd-L-OH), respectively. At a ligand concentration of 24 μM, H4L-OEt and H4L-OH showed negligible luminescent quenching by RR- and SS-hydrobenzoin (HB) enantiomers with Stern-Völmer constants of 29-89 M-1. In contrast, CMOFs displayed efficient quenching by HB enantiomers with Stern-Völmer constants of 583-1200 M-1, due to significant HB preconcentration in CMOF channels via favorable host-guest interactions between CMOF frameworks and HB molecules. The CMOFs demonstrated luminescence quenching selectivity for RR-HB over SS-HB, with Zn-L-OEt exhibiting the highest quenching ratio (Ksv(RR)/Ksv(SS)) of 1.624. This work highlights the potential of CMOFs in enantioselective sensing applications.
Published Version
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