Peculiar Triarylamine-Based Co-assembled Supramolecular Polymers That Exhibit Two Transition Temperatures in the Formation of a Coiled Helical Bundle.

This paper describes the peculiar co-assembly supramolecular polymerization behavior of triphenylamine trisamide derivatives with d-alanine (T-ala) or glycine (T-gly) moieties. Concentration and temperature-dependent circular dichroism (CD) spectroscopy revealed that the heating curves of co-assemblies obtained at various molar ratios of T-ala to T-gly exhibited two distinct transition temperatures. The first transition was due to the transformation from coiled helical bundles to single helical fibers without handedness. The second was due to a change from typical elongation to nucleation. These phenomena were confirmed by solvent-dependent decoiling of coiled helical structures and concentration-dependent morphological analysis. The two transitioning temperatures were dependent on the concentration of T-ala in the co-assemblies, suggesting that T-ala concentration plays an important role in the formation of coiled helical bundles. Our study demonstrated the first observation of two distinct transition temperatures in supramolecular polymers.