Encoding and Expressing the Handedness of a Möbius π System in a Totemic Architecture

The efficient control of the chirality of Möbius π systems remains a challenging task that hinders the development of such molecules into information processing systems. Achieving such control through a redox process would thus open new opportunities. In this context, redox behaviors of Ni(II) and Pd(II) complexes of a Möbius aromatic [28]hexaphyrin doubly linked to an α-cyclodextrin have been investigated. This totemic architecture embedding three types of chirality elements generates two pseudoenantiomers after coordination with either metal. These isomeric pairs possess marked and opposite chiroptical signatures resulting from the P and M configurations of the Möbius π systems. Chemical oxidation to 26-π systems led to behaviors reminiscent to The Oak and the Reeds fable, due to a N3C coordination sphere of Ni(II) being more robust than that of Pd(II). Oxidized Ni(II) complexes (the Oak) maintain a Möbius-type conformation at the expense of the π-systems, which undergo an interruption due to inevitable water insertion. In contrast, oxidation of Pd(II) complexes (the Reeds) converts the Möbius aromatic systems into Hückel (rectangular) aromatic ones that are maintained in the chiral environment provided by the linking pattern with the cyclodextrin. This constitutes an effective chiral instructing site, as reduction back to their original Möbius configuration occurs with high stereoselectivity. Such a reversible shape-shifting process corresponds to a chiral memory phenomenon where the handedness of a cyclic π system is encoded in a scaffold and expressed upon changing an electronic state. For both metals, spectroelectrochemical studies ultimately revealed robust ON-OFF chiroptical switches, which is unprecedented with Möbius π-systems.