Mechanosensitive non-equilibrium supramolecular polymerization in closed chemical systems.

Chemical fuel-driven supramolecular systems have been developed showing out-of-equilibrium functions such as transient gelation and oscillations. However, these systems suffer from undesired waste accumulation and they function only in open systems. Herein, we report non-equilibrium supramolecular polymerizations in a closed system, which is built by viologens and pyranine in the presence of hydrazine hydrate. On shaking, the viologens are quickly oxidated by air followed by self-assembly of pyranine into micrometer-sized nanotubes. The self-assembled nanotubes disassemble spontaneously over time by the reduced agent, with nitrogen as the only waste product. Our mechanosensitive dissipative system can be extended to fabricate a chiral transient supramolecular helix by introducing chiral-charged small molecules. Moreover, we show that shaking induces transient fluorescence enhancement or quenching depending on substitution of viologens. Ultrasound is introduced as a specific shaking way to generate template-free reproducible patterns. Additionally, the shake-driven transient polymerization of amphiphilic naphthalenetetracarboxylic diimide serves as further evidence of the versatility of our mechanosensitive non-equilibrium system.