Network Formation in an Orthogonally Self-Assembling System

Many supramolecular motifs self-assemble into nanorods, forming the basis of the mechanical properties of supramolecular polymers. When integrated as end-caps in a bifunctional telechelic polymer, the motifs can phase segregate into the same or into another nanorod. In the latter case, a functional cross-link is formed by the bridging chain that strengthens the polymer network. This study introduces a supramolecular polymeric system that consists of two different nanorod forming supramolecular motifs. When end-capped to monofunctional polymers, these supramolecular motifs self-assemble in an orthogonal fashion in two separate types of noncross-linked nanorods, resulting in a viscous liquid lacking macroscopic properties. The addition of 15 mol % of an α,ω-telechelic polymer containing both supramolecular motifs, each on one end, transforms this viscous sticky liquid to a solid material with elastomeric properties due to network formation between the two types of nanorods.