Selective chiral dimerization and folding driven by arene–perfluoroarene force

Abstract

Oligomerization and folding of chiral compounds afford diversified chiral molecular architectures with interesting chiroptical properties, but their rational and precise control remain poorly understood. In this work, we employed arene–perfluoroarene (AP) interaction to manipulate the folding and dimerization of alanine derivatives bearing pyrene and a perfluoronaphthalene derivative. Based on X-ray crystallography and nuclear magnetic resonance, the compound with a smaller tether and high skeleton rigidity self-assembled into double helical dimers by duplex hydrogen bonding and AP forces in a less polar solvent. Reversible disassociation occurred upon switching to a dipolar solvent or applying heating–cooling cycles. In comparison, the compound with increased skeleton flexibility folds into chiral molecular clamps in a less polar solvent, and is transformed into planar dimers upon switching to a polar solvent. The dynamic geometrical transformation between dimerization and folding was accompanied by chiroptical switching. Beyond the molecular and supramolecular level, we showed hierarchy control in the self-assembled nanoarchitectures and columnar and lamellar arrangements of their molecular packing. This work utilized AP forces to prepare and manipulate the chiral architectures at different hierarchical levels, enriching methodologies in precise chiral synthetic chemistry.