Host-Enhanced Phenyl-Perfluorophenyl Polar-π Interactions.

Phenyl-perfluorophenyl polar-π interactions have been revisited for the design and fabrication of functional supramolecular systems. The relatively weak associative interactions (ΔG ≈ -1.0 kcal/mol) have limited their use in aqueous self-assembly to date. Herein, we propose a strategy to strengthen phenyl-perfluorophenyl polar-π interactions by encapsulation within a synthetic host, thus increasing the binding affinity to ΔG= -15.5 kcal/mol upon formation of heteroternary complexes through social self-sorting. These heteroternary complexes were used as dynamic, yet strong, cross-linkers in the fabrication of supramolecular gels, which exhibited excellent viscoelasticity, stretchability, self-recovery, self-healing, and energy dissipation. This work unveils a general approach to exploit host-enhanced polar-π interactions in the design of robust aqueous supramolecular systems.Z. H. thanks Marie Skłodowska- Curie Fellowship (H2020-MSCA-IF-2018, 845640). X.C. ac- knowledges CDT for financial support. D.W. thanks EPSRC PhD studentship (EP/R512461/1). G.W., J.A.M & O.A.S. acknowledge ERC consolidator grant (CAM-RIG, 726470) and EPSRC Programme Grant (NOtCH, EP/L027151/1) for financial support. We thank Dr. Robin Antrobus (Cam- bridge Institute for Medical Research) for help with MS