Host-Enhanced Phenyl-Perfluorophenyl Polar−π Interactions

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 selfassembly 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.

Cucurbit[n]urils for Supramolecular Catalysis

“…CB [8] is the most widely utilized supramolecular nanoreactor owing to its appropriate size and strong affinity for containing two or more guests homogeneously or heterogeneously. [23,24] In 1983, Mock and co-workers first reported the CB [6] catalyzed 1,3 dipolara zide-alkynec ycloaddition( AAC) reaction. [25,26] The azide andt he alkyne groups were encapsulatedi nt he cavity of CB [6],a nd the amino groups helped to stabilize the host-guestc omplex( Figure3).…”

Light-intensity switch enabled nonsynchronous growth of fluorinated raspberry-like nanoparticles

“…5d, e and S22 †), exhibiting an enhanced uorescence at 430 nm and a blue-shi of 40 nm compared to TPE-COOH due to restricted intramolecular rotation. 56,57 The successful incorporation of TPE-COOH is probably due to the polar-p interaction 58,59 between -C 6 F 5 from the host particle and phenyl from the TPE guest (Fig. 5f).…”

Supramolecular hydrogels prepared from fluorescent alkyl pyridinium acrylamide monomers and CB[8]

“…[21][22][23] We also demonstrated that this benzyl-imidazolium motif could be simultaneously bound with a perfluorophenyl moiety forming strong polar-π interactions within CB [8] mediated hydrogels. 24 Similarly, Zhang et al demonstrated that an inclusion complex formed from an ester derivative of the tripeptide Phe-Gly-Gly and CB [8] could be polymerised to form both supramolecular hydrogels and microgels. 25,26 They noted that supramolecular hydrogels formed using this approach were significantly more mechanically robust than their counterparts produced by first synthesising the polymers and then forming the CB [8] complex (a phenomenon which was suggested to be a result of the viscous polymer solution limiting CB [8] diffusion).…”