Hypervalent Iodine(III) Mediated Halogen Bonded Supramolecular Chiral System with Cholesteryl Naphthalimides

Abstract

AbstractHalogen bonding acknowledged as a noteworthy weak interaction, has gained growing recognition in the field of supramolecular chemistry. In this study, we selected structurally rigid diaryliodonium ions (I(III)) with two biaxial σ‐holes as halogen‐bond donors, to bind with three chiral acceptor molecules bearing cholesteryl and naphthalimides with distinct geometries. The abundant carbonyl oxygen atoms in side‐arm substituents function as multiple acceptors for halogen bonding. The self‐aggregation of chiral acceptor molecules demonstrates adaptiveness to solvent media, evidenced by the inversion of the Cotton effect and the morphological evolution from spherical to rod‐like nanoarchitectures in different solvent systems. The distinct geometries of the acceptor molecules conferred various binding modes with I(III). The introduction of I(III) as a halogen‐bond donor regulates the aggregation of the donors, achieving amplification of chiroptical signals and inheriting solvent responsiveness from the self‐aggregated assembly. This study successfully utilized rational structural design and multimodal control strategies to achieve regulation of supramolecular chirality.