Chiral metal-organic frameworks (MOFs) with porous and tunable natures have made them feasible for performing a variety of chemical reactions as heterogeneous asymmetric catalysts. By incorporating the oxidation catalyst [BW12O40](5-) and the chiral group, L- or D-pyrrolidin-2-ylimidazole (PYI), into one single framework, the two enantiomorphs Ni-PYI1 and Ni-PYI2 were obtained via self-assembly, respectively. The channels of Ni-PYIs were enlarged through a guest exchange reaction to remove the cationic chiral templates and were well modulated with hydrophilic/hydrophobic properties to allow molecules of both H2O2 and olefin ingress and egress. The coexistence of both the chiral directors and the oxidants within a confined space provided a special environment for the formation of reaction intermediates in a stereoselective fashion with high selectivity. The resulting MOF acted as an amphipathic catalyst to prompt the asymmetric dihydroxylation of aryl olefins with excellent stereoselectivity.

Currently, great interest is focused on developing auto-tandem catalytic reactions; a substrate is catalytically transferred through mechanistically distinct reactions without altering any reaction conditions. Here by incorporating a pyrrolidine moiety as a chiral organocatalyst and a polyoxometalate as an oxidation catalyst, a powerful approach is devised to achieve a tandem catalyst for the efficient conversion of CO2 into value-added enantiomerically pure cyclic carbonates. The multi-catalytic sites are orderly distributed and spatially matched in the framework. The captured CO2 molecules are synergistically fixed and activated by well-positioned pyrrolidine and amine groups, providing further compatibility with the terminal W=O activated epoxidation intermediate and driving the tandem catalytic process in a single workup stage and an asymmetric fashion. The structural simplicity of the building blocks and the use of inexpensive and readily available chemical reagents render this approach highly promising for the development of practical homochiral materials for CO2 conversion.

A new approach to merge Cu-catalysis/Ru-photocatalysis within one single MOF was achieved by incorporating [SiW11O39Ru(H2O)]5– into Cu–BPY MOFs.