From Weakness to Strength: C–H/π-Interaction-Guided Self-Assembly and Gelation of Poly(benzyl ether) Dendrimers

The C–H/π interactions
as the key driving force for
the construction of supramolecular gels remain a great challenge because
of their weak nature. We hereby employed for the first time weak C–H/π
interactions for the construction of supramolecular dendritic gels
based on peripherally methyl-functionalized
poly­(benzyl ether) dendrimers. Their gelation property is highly dependent
on the nature of the peripheral methyl groups. Furthermore, single-crystal
X-ray analysis and NMR spectroscopy revealed that multiple C–H/π
interactions between the proton of the methyl group and the electron-rich
peripheral methyl-substituted aryl ring played significant roles in
the formation of supramolecular nanofibers and organogels. This study
uncovers the critical role of weak noncovalent interactions and provides
new insights into the further design of self-assembled nanomaterials.