Clay Nanosheet‐Based Nanocomposite Supramolecular Hydrogel Enabling Rapid, Reversible Phase Transition Only with Visible Light

High mechanical properties and rapid sol/gel phase transition are mutually exclusive in the hydrogels reported to date, most likely because the 3D crosslinked networks of mechanically robust hydrogels comprise bundled thick fibers that are not rapidly dissociable or formable. Herein, we report a visible light-responsive hydrogel that showed a rapid, reversible sol/gel phase transition despite its relatively high mechanical properties (storage modulus ~10³ Pa). To construct its 3D crosslinked network, we used a design strategy analogous to that employed for our highly water-rich yet mechanically robust nanocomposite supramolecular hydrogel ("aqua material"). In this case, multiple poly(ethylene glycol) chains carrying ortho-tetramethoxyazobenzene termini (^AzoPEG) were noncovalently crosslinked by clay nanosheets (CNSs) with surface-immobilized β-cyclodextrin units using their seven guanidinium ion (Gu⁺) pendants (^GuCD) via a multivalent salt-bridge. When exposed to visible light at 625 and 450 nm, the azobenzene termini isomerized from trans-to-cis and cis-to-trans, respectively, and were detached from and attached to the surface-immobilized ^GuCD units. The advantage of this CNS-based nanocomposite supramolecular system is its simple 3D network structure, which forms and breaks rapidly without slow chain entangling and disentangling processes.