Cooling Dodecanethiol-Capped 2 nm Diameter Gold Nanocrystal Superlattices below Room Temperature Induces a Reversible Order–Disorder Structure Transition

We recently observed that a disordered assembly of octadecanethiol-capped gold (Au) nanocrystals can order when heated from room temperature to 60 °C [Yu, Y.; Jain, A.; Guillaussier, A.; Voggu, V. R.; Truskett, T. M.; Smilgies, D.-M.; Korgel, B. A. <i>Faraday Discuss.</i> <b>2015</b>, <i>181</i>, 181–192]. This “inverse melting” structural transition was reversible and occurred near the melting-solidification temperature of the capping ligands. To determine the generality of this phenomenon, we studied by in situ grazing incidence small-angle X-ray scattering (GISAXS) the structure of assemblies of Au nanocrystals with shorter C<sub>12</sub> and C<sub>5</sub> alkanethiol capping ligands that form ordered superlattices at room temperature and have a ligand melting-solidification temperature below room temperature. Superlattices of dodecanethiol-capped Au nanocrystals disorder when cooled below 260 K, which is the melting-solidification temperature for dodecanethiol. Au nanocrystals capped with even shorter pentanethiol ligands that have a melting transition below 100 K (the lowest experimentally accessible temperature) do not undergo the disorder transition.