Stimuli-Responsive Properties of Supramolecular Gels Based on Pyridyl-N-oxide Amides

Abstract

The nature of functional groups and their relative position and orientation play an important role in tuning the gelation properties of stimuli-responsive supramolecular gels. In this work, we synthesized and characterized mono-/bis-pyridyl-N-oxide compounds of N-(4-pyridyl)nicotinamide (L 1–L 3). The gelation properties of these N-oxide compounds were compared with the reported isomeric counterpart mono-/bis-pyridyl-N-oxide compounds of N-(4-pyridyl)isonicotinamide. Hydrogels obtained with L 1 and L 3 were thermally and mechanically more stable than the corresponding isomeric counterparts. The surface morphology of the xerogels of di-N-oxides (L 3 and diNO) obtained from the water was studied using scanning electron microscopy (SEM), which revealed that the relative position of N-oxide moieties did not have a prominent effect on the gel morphology. The solid-state structural analysis was performed using single-crystal X-ray diffraction to understand the key mechanism in gel formation. The versatile nature of N-oxide moieties makes these gels highly responsive toward an external stimulus, and the stimuli-responsive behavior of the gels in water and aqueous mixtures was studied in the presence of various salts. We studied the effect of various salts on the gelation behavior of the hydrogels, and the results indicated that the salts could induce gelation in L 1 and L 3 below the minimum gelator concentration of the gelators. The mechanical properties were evaluated by rheological experiments, indicating that the modified compounds displayed enhanced gel strength in most cases. Interestingly, cadmium chloride formed supergelator at a very low concentration (0.7 wt% of L 3), and robust hydrogels were obtained at higher concentrations of L 3. These results show that the relative position of N-oxide moieties is crucial for the effective interaction of the gelator with salts/ions resulting in LMWGs with tunable properties.