Preferential molecular recognition of heterochiral guests within a cyclophane receptor

The discrimination of enantiomers by natural receptors is a well-established phenomenon. In contrast the number of synthetic receptors with the capability for enantioselective molecular recognition of chiral substrates is scarce and for chiral cyclophanes indicative for a preferential binding of homochiral guests. Here we introduce a cyclophane composed of two homochiral core-twisted perylene bisimide (PBI) units connected by p-xylylene spacers and demonstrate its preference for the complexation of [5]helicene of opposite helicity compared to the PBI units of the host. The pronounced enantio-differentiation of this molecular receptor for heterochiral guests can be utilized for the enrichment of the P-PBI-M-helicene-P-PBI epimeric bimolecular complex. Our experimental results are supported by DFT calculations, which reveal that the sterically demanding bay substituents attached to the PBI chromophores disturb the helical shape match of the perylene core and homochiral substrates and thereby enforce the formation of syndiotactic host-guest complex structures. Hence, the most efficient substrate binding is observed for those aromatic guests, e. g. perylene, [4]helicene, phenanthrene and biphenyl, that can easily adapt in non-planar axially chiral conformations due to their inherent conformational flexibility. In all cases the induced chirality for the guest is opposed to those of the embedding PBI units, leading to heterochiral host-guest structures. The design of synthetic supramolecular receptors capable of enantioselective molecular recognition is challenging. Here the authors report a perylene bisimide-based receptor that forms heterochiral host-guest complexes upon aromatic guests encapsulation; guest recognition can be modulated by peripheral substitution of the binding site.

Automated summary

The discrimination of enantiomers by natural receptors is a well-established phenomenon, but the number of synthetic receptors with enantioselective molecular recognition capability is limited. In this study, a cyclophane composed of homochiral perylene bisimide (PBI) units was shown to preferentially bind [5]helicene of opposite helicity compared to the PBI units of the host. The enantio-differentiation of this molecular receptor for heterochiral guests can be utilized for the enrichment of specific bimolecular complex. The design of synthetic supramolecular receptors capable of enantioselective molecular recognition is challenging, and this study presents a novel approach using perylene bisimide-based receptors.