Host-Enhanced Phenyl-Perfluorophenyl Polar-π Interactions.

Zehuan Huang,Jade A Mccune,Guanglu Wu,Pierangelo Metrangolo,Oren A Scherman,Daniel Whitaker,Xiaoyi Chen

doi:10.1021/jacs.0c02275

Zehuan Huang, Jade A Mccune + Show 5 more

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https://doi.org/10.1021/jacs.0c02275

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Abstract

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.

Highlights

Phenyl-perfluorophenyl polar−π interactions have been revisited for the design and fabrication of functional supramolecular systems
Fluorinated small molecules and macromolecules have been widely utilized in organic synthesis,1,2 polymer science,3 medicinal chemistry,4,5 drug delivery,6 liquid crystals,7 and supramolecular chemistry.8−11 Noncovalent interactions between aromatic molecules are important in both natural and artificial supramolecular systems
Phenyl-perfluorophenyl polar−π interactions are an elegant example of electrostatic reinforcement. This interaction emerged from the first discovery of a 1:1 cocrystal of hexafluorobenzene and benzene in 196015 (Figure 1a) followed by structural elucidation in 1992 by William et al

Summary

Introduction

Phenyl-perfluorophenyl polar−π interactions have been revisited for the design and fabrication of functional supramolecular systems. We utilized the 5FBVI-BVI-CB[8] complex as a supramolecular cross-linker for fabricating robust transparent polyacrylamide networks exhibiting excellent mechanical properties and ionic conductivity.

Results

Conclusion