Electron transport through supercrystals of atomically precise gold nanoclusters: a thermal bi-stability effect

Nanoparticles (NPs) may behave like atoms or molecules in the self-assembly into artificial solids with stimuli-responsive properties. However, the functionality engineering of nanoparticle-assembled solids is still far behind the aesthetic approaches for molecules, with a major problem arising from the lack of atomic-precision in the NPs, which leads to incoherence in superlattices. Here we exploit coherent superlattices (or supercrystals) that are assembled from atomically precise Au₁₀₃S₂(SR)₄₁ NPs (core dia. = 1.6 nm, SR = thiolate) for controlling the charge transport properties with atomic-level structural insights. The resolved interparticle ligand packing in Au₁₀₃S₂(SR)₄₁-assembled solids reveals the mechanism behind the thermally-induced sharp transition in charge transport through the macroscopic crystal. Specifically, the response to temperature induces the conformational change to the R groups of surface ligands, as revealed by variable temperature X-ray crystallography with atomic resolution. Overall, this approach leads to an atomic-level correlation between the interparticle structure and a bi-stability functionality of self-assembled supercrystals, and the strategy may enable control over such materials with other novel functionalities.