Polyrotaxane-Mediated Self-Assembly of Gold Nanospheres into Fully Reversible Supercrystals

The use of a thiol‐functionalized nonionic surfactant to stabilize spherical gold nanoparticles in water induces the spontaneous formation of polyrotaxanes at the nanoparticle surface in the presence of the macrocycle α‐cyclodextrin. Whereas using an excess of surfactant an amorphous gold nanocomposite is obtained, under controlled drying conditions the self‐assembly between the surface supramolecules provides large and homogenous supercrystals with hexagonal close packing of nanoparticles. Once formed, the self‐assembled supercrystals can be fully redispersed in water. The reversibility of the crystallization process may offer an excellent reusable material to prepare gold nanoparticle inks and optical sensors with the potential to be recovered after use. A golden get‐together: A thiol‐functionalized nonionic surfactant and α‐cyclodextrin undergo complexation at the surface of gold nanoparticles to form polyrotaxane‐stabilized nanocrystals. Under controlled drying conditions, the nanocrystals can reversibly self‐assemble into homogenous hexagonal closed‐packed supercrystals.