Thermodynamic Description of Bis-urea Self-Assembly: Competition between Two Supramolecular Polymers

Supramolecular polymers are chains of small molecules held together through reversible noncovalent interactions. In general, a given monomer self-assembles into a single type of supramolecular polymer. However, in a few cases, two different self-assembled structures can coexist; this yields interesting responsive systems. To improve the understanding of these systems, we report an association model describing the self-assembly of a supramolecular polymer into two competing forms. The parameters controlling the system were measured by high sensitivity differential scanning calorimetry and isothermal titration calorimetry in the case of a hydrogen-bonded bis-urea supramolecular polymer solution in toluene. The model enables us to compute the proportion and length of all components in the system at any temperature and concentration. The results of these calculations are in agreement with the experimental phase diagram and with independent viscosity measurements.