Suspending Polyrotaxane Dissociation via Photo-Reversible Capping of Terminals.

Reversible covalent bonds yield polymeric materials with functional characteristics such as self-healing, shape memory, stress relaxation, and stimuli-responsiveness. Here, photo-reversibly cappable polyrotaxanes are designed and the on-off controlled dissociation of their supramolecular architectures is demonstrated. The polyrotaxanes are synthesized by capping dithiobenzoates at both terminals of polyethylene glycol threaded through multiple α-cyclodextrins. Since dethreading of the α-cyclodextrins is prevented by the dithiobenzoate stoppers, the supramolecular dissociation is induced by their photo-cleavage. Subsequently, the cleaved dithiobenzoates spontaneously re-cap the polyrotaxane terminals in darkness. Thus, the supramolecular dissociation can be modulated by photo-reversible capping of the dithiobenzoate stoppers. These polyrotaxanes with dithiobenzoate stoppers are promising functional materials for photo-controlling physical properties and structures.