Modulating Noncovalent Cross-links with Molecular Switches.

Spiropyran molecular switches, in conjunction with transition metal ions, are shown to operate as reversible polymer cross-linkers. Solutions containing a spiropyran-functionalized polymer and transition metal ions underwent reversible thermally triggered (light-triggered) transient network formation (disruption) driven by the association (dissociation) of metal-ligand cross-links. Heat triggers metal-ion-mediated cross-linking via thermal isomerization of spiropyran to its open, merocyanine form, and exposure to visible light triggers dissociation of polymer cross-links. Cross-linking is found to depend on both the valence of the ion as well as the molar ratio of spiropyran to metal salt. We envision this to be a starting point for the design of many types of reversible, stimuli-responsive polymers, utilizing the fact that spiropyrans have been shown to respond to a variety of stimuli including heat, light, pH, and mechanical force.