Preprogrammed assembly of supramolecular polymer networks via the controlled disassembly of a metastable rotaxane

Preassembled materials are ubiquitous in our everyday life due to their readiness and functionality; an end-user simply follows instructions to assemble them and harness function. Here, metastable rotaxanes are utilized to approach preassembled materials: a multicomponent, preprogrammed system can be conveniently (via heating) transformed into colorful polymer networks at the end-user's will. In our daily life, some of the most valuable commodities are preprogrammed or preassembled by a manufacturer; the end-user puts together the final product and gathers properties or function as desired. Here, we present a chemical approach to preassembled materials, namely supramolecular polymer networks (SPNs), which wait for an operator's command to organize autonomously. In this prototypical system, the controlled disassembly of a metastable interlocked molecule (rotaxane) liberates an active species to the medium. This species crosslinks a ring-containing polymer and assembles with a reporting macrocycle to produce colorful SPNs. We demonstrate that by using identical preprogrammed systems, one can access multiple supramolecular polymer networks with different degrees of fluidity (mu* = 2.5 to 624 Pa s(-1)) and color, all as desired by the end-user.