Chemoresponsive Supramolecular Polypseudorotaxanes with Infinite Switching Capability

Abstract Chemoresponsive supramolecular systems with infinite switching capability are important for applications in recycled materials and intelligent devices. To attain this objective, here a chemoresponsive polypseudorotaxane is reported on the basis of a bis( p ‐phenylene)‐34‐crown‐10 macrocycle ( H ) and a cyano‐substituted viologen guest ( G ). H and G form a [2]pseudorotaxane ( H ⊃ G ) both in solution and in the solid state. Upon addition of AgSF 6 , a polypseudorotaxane (denoted as [ H⋅G⋅ Ag] n ) forms as synergistically driven by host–guest complexation and metal‐coordination interactions. [ H⋅G⋅ Ag] n depolymerizes into a [3]pseudorotaxane (denoted as H 2 ⋅G⋅ Ag 2 ⋅ acetone 2 ) upon addition of H and AgSF 6 , while it reforms with successive addition of G . The transformations between [ H⋅G⋅ Ag] n and H 2 ⋅G⋅ Ag 2 ⋅ acetone 2 can be switched for infinite cycles, superior to the conventional chemoresponsive supramolecular polymeric systems with limited switching capability.