Hypervalent Iodine (III)‐Based Complexation for Chiroptical Supramolecular Glass, Deep Eutectic Solvent and Luminescent Switch

Abstract

Hypervalent iodine(III) have widely been utilized for organic synthetic reagents. They are also recognized as positive charge‐assisted, exceptionally robust biaxial halogen bond donors, while their potential in supramolecular materials is barely explored. This work reports a cyclic diaryliodonium ion as biaxial halogen bonding donor that displays remarkable binding affinity toward phenanthroline or acridine acceptors with chiral pendants. Biaxial halogen bonding enables chiroptical evolution in solution, allowing for rational control over supramolecular chirality. Leveraging their strong binding affinity, the halogen bonding complexes manifested amorphous properties and deep eutectic behavior in the solid state. Capitalizing on these attributes, this work achieves the successful preparation of supramolecular glasses and deep eutectic solvents. Additionally, halogen bonding appended light irradiation‐triggered luminescence through a hydrogen atom transfer process, showing applications in anti‐counterfeit and display.