High-Enantioselectivity Adsorption Separation of Racemic Mandelic Acid and Methyl Mandelate by Robust Chiral UiO-68-Type Zr-MOFs.

Abstract

Mandelic acid and its analogues are highly valuable medical intermediates and play an important role in the pharmaceutical industry, biochemistry, and life sciences. Therefore, effective enantioselective recognition and separation of mandelic acid are of great significance. In this study, two of our recently reported chiral amine-alcohol-functionalized UiO-68-type Zr-HMOFs 1 and 3 with high chemical stability, abundant binding sites, and large chiral pores were selected as chiral selectors for the enantioselective separation of mandelic acid (MA), methyl mandelate (MM), and other chiral molecules containing only one phenyl. Materials 1 and 3 exhibited excellent enantioselective separation performance for MA and MM. Especially for the separation of racemate MA, the enantiomeric excess values reached 97.3 and 98.9%, which are the highest reported values so far. Experimental and density functional theory (DFT) computational results demonstrated that the introduction of additional phenyls on the chiral amine alcohol pendants in 3 had somewhat impact on the enantioselective adsorption and separation of MA or MM compared with 1, but it was not significant. Further research on the enantioselective separation of those chiral adsorbates containing only one phenyl by material 1 indicated the crucial role of the groups directly bonded to the chiral carbons of the adsorbates in the selective separation of enantiomers, especially showing higher enantioselectivity for the adsorbates with two hydrogen-bonding groups directly bonded to its chiral carbon.