Utilization of a combination of weak hydrogen-bonding interactions and phase segregation to yield highly thermosensitive supramolecular polymers

Supramolecular polymerization, i.e., the self-assembly of polymer-like materials through the utilization of the noncovalent bond, is a developing area of research. In this paper, we report the synthesis and investigation of nucleobase-terminated (N-6-anisoyl-adenine and N-4-(4-tert-butylbenzoyl)cytosine) low molecular weight poly(THF) macromonomers (< 2000 g mol(-1)). Even though the degree of interaction between the nucleobase derivatives is very low (< 5 M-1) these macromonomers self-assemble in the solid state to yield materials with film and fiber-forming capability. While the mechanical properties of films of both materials show extreme temperature sensitivity, resulting in the formation of very low viscosity melts, they do behave differently, which is attributed to the nature of the self-assembly controlled by the nucleobase. A combination of FT-IR, WAXD, and rheological experiments was carried out to further investigate the nature of the self-assembly in these systems. The studies demonstrate that a combination of phase segregation between the hard nucleobase chain ends and the soft poly(THF) core combined with aromatic amide hydrogen bonding is utilized to yield the highly thermosensitive supramolecular polymeric materials. In addition, analysis of the data suggests that the rheological properties of these supramolecular materials is controlled by the disengagement rate of the nucleobase chain ends from the "hard" phase, which, if shown to be general, provides a design criteria in the development of more thermally responsive materials.