A compact catenane with tuneable mechanical chirality

Abstract

Catenanes are formed by the mechanical interlocking of two or more rings. Enantiomers of a catenane can exist even if the rings themselves are achiral. Here we demonstrate that two achiral rings, each featuring a polarized cavity and two mirror planes, in addition to a two-fold axis of symmetry, can form a catenane with mechanical chirality. The catenane has been designed using an isostructural desymmetrization strategy, enabling the catenane to adopt a compact co-conformation similar to that of its achiral isostructural counterpart. Mechanical chirality in the catenane occurs when its two rings become interlocked in the compact co-conformation, leading to the loss of the two planes of symmetry present in its individual rings. The resulting enantiomers, which both have two-fold axes of symmetry, exist as a racemic modification in the solid state. Dynamic 1H NMR spectroscopy carried out in acetonitrile-d3 reveals a barrier of 16.4 kcal mol−1 to racemization between the two enantiomeric catenanes, the equilibrium of which can be influenced by the addition of chiral disulfonate anions, which support induced chirality and exhibit optical activity. One of the salts crystallizes to give only one diastereoisomer in the solid state. This research highlights the potential of using the isostructural desymmetrization strategy to create and study mechanical chirality along with its properties. Catenanes can exhibit chirality even when their component rings are achiral. Here an isostructural desymmetrization strategy is developed, demonstrating that two achiral rings, each featuring two mirror planes and a two-fold axis of symmetry, can form a catenane with tuneable mechanical chirality.