Counter Cation Dependent and Stimuli Responsive Supramolecular Polymers Constructed by Calix[4]pyrrole Based Host–Guest Interactions

Abstract

Carboxylate tethered calix[4]pyrroles in the form of their tetrabutylammonium (TBA) and cetyltrimethylammonium (CTA) salts were synthesized via an acid base reaction between the corresponding carboxylic acid functionalized calix[4]pyrrole and tetrabutyl‐ or cetyltrimethylammonium hydroxide. The host–guest recognition motif based on these calix[4]pyrrole macrocycles and tethered carboxylate units was employed to construct novel A–B type supramolecular polymers from low molecular weight monomers in chloroform. These supramolecular polymers were found to be dependent on the counter cation in terms of the properties of supramolecular polymers. 1H‐, DOSY‐, NOESY‐NMR spectroscopic analyses, viscosity measurements, and SEM results were used to characterize supramolecular polymers and revealed that the CTA cation becomes a direct part of supramolecular polymer via cation–π interactions between the ammonium part of CTA and carboxylate‐bound calix[4]pyrrole, effecting the overall properties of supramolecular polymers such as viscosity, gel formation, and drawing fibers. Additionally, reversible pH‐ and thermo‐responsiveness of the supramolecular polymers were demonstrated for the first time for an anion recognition induced calix[4]pyrrole based supramolecular polymer.