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We have analyzed the nature and role of functional groups on the self-assembly modes and the physical properties of multicomponent gels with structurally similar individual components. The gelation properties of individual and mixed enantiomeric compounds of biphenyl bis-(amides) of alanine (BPA) or phenylalanine (BPP) methyl ester were analyzed in various solvent/solvent mixtures. Multicomponent gels were formed by mixing the enantiomeric BPP compounds at a lower concentration, but a higher concentration was required for mixed alanine-based BPA gels. The comparison of the mechanical strength of the individual and mixed BPP compounds indicated that the mixed BPP gels displayed enhanced mechanical strength (∼2-fold increase) in p-xylene, but a weaker gel was observed in DMSO/water. However, a reverse trend was observed for BPA gels, indicating the role of functional groups in the gel network formation. X-ray diffraction analysis of the gelator and the xerogels in the solid state confirmed the formation of co-assembled networks in mixed enantiomeric gels. The stability of the gels towards anions was evaluated by analyzing the anion induced stimuli-responsive properties. These results indicate the effective modeling of the functional groups of the individual components could lead to multicomponent gels with tunable properties., (© 2023 Wiley-VCH GmbH.)

The structural modification of existing supramolecular architecture is an efficient strategy to design and synthesize supramolecular gels with tunable and predictable properties. In this work, we have modified bis(pyridyl urea) compounds with different linkers, namely hexylene and butylene, to their corresponding bis(pyridyl- N -oxide urea). The gelation properties of both the parent and the modified compounds were studied, and the results indicated that modification of the 3-pyridyl moieties to the corresponding 3-pyridyl- N -oxides induced hydrogelation. The stability of the parent and modified compounds were evaluated by sol-gel transition temperature ( T gel ) and rheological measurements, and single-crystal X-ray diffraction was used to analyze the solid-state interactions of the gelators. The morphologies of the dried gels were analyzed by scanning electron microscopy (SEM), which revealed that the structural modification did not induce any prominent effect on the gel morphology. The stimuli-responsive behavior of these gels in the presence of salts in DMSO/water was evaluated by rheological experiments, which indicated that the modified compounds displayed enhanced gel strength in most cases. However, the gel network collapsed in the presence of the chloride salts of aluminum(III), zinc(II), copper(II), and cadmium(II). The mechanical strength of the parent gels decreased in the presence of salts, indicating that the structural modification resulted in robust gels in most cases. The modified compounds formed gels below minimum gel concentration in the presence of various salts, indicating salt-induced gelation. These results show the making and breaking ability of the gel network in the presence of external stimuli (salts), which explains the potential of using LMWGs based on N -oxide moieties as stimuli-responsive materials.