The thermodynamic stability of assemblies formed by a bis-urea-based supramolecular polymer, 2,4-bis(2-ethylhexylureido)toluene (EHUT), was investigated in solutions using either benzene or toluene as the solvent. Starting from a higher temperature in which EHUT was soluble in both solvents, molecules spontaneously self-organized into tubular assemblies upon cooling and these assemblies were stable in a wide range of temperatures. However, the systems followed different paths below a specific temperature: while the supramolecular polymer remained stable in toluene, EHUT molecules underwent precipitation in benzene. The causes for these different behaviors were explored by molecular dynamics simulations, which provided support for stronger enthalpic stabilization of the tubular assemblies in toluene as compared to benzene. This stabilization was due mainly to the better interaction energy of trapped toluene molecules instead of benzene ones. For both cases, lowering the temperature makes the solvent penetration inside the tubes less favorable, which reduces the stability of supramolecular structures upon cooling. Graphical abstract Different EHUT solubilities.
Keywords: Bis-urea; Molecular dynamics simulations; Self-assembling; Solvent effects; Solvent pockets; Supramolecular polymers.