摘要： Cation exchange is a versatile post-synthetic technique that has been exploited in the synthesis of metastable nanocrystals through preservation of the anion sublattice. Here we report on the mechanistic details of the synthesis of metastable Au2S via cation exchange with Cu2-xS nanocrystals. This conversion requires a transformation of the anion sublattice, from hcp in Cu2-xS to bcc Au2S accompanied by an expansion of the unit cell. The ligand environment plays a key role in the driving force of the reaction as the presence of oleylamine allows the conversion to proceed at room temperature while the addition of trioctylphosphine hinders the reaction. By employing transmission electron microscopy (TEM) on faceted nanocrystals and partial cation exchange of nanocrystals, it was demonstrated that the reaction proceeds in a highly directional manner through the pyramidal facets. Since cation exchange produces high quality nanocrystals as seen through XRD and TEM, UV-Vis and Raman spectroscopy were used to characterize the optoelectronic properties of the metastable Au2S nanocrsytals. A Tauc plot analysis revealed a band gap of 2.6 eV, while two intrinsic Raman modes were identified at 265 cm-1 and 329 cm-1. Density functional theory (DFT) calculations of structures, energy bands, optical spectra, and phonon spectra were performed and combined with the experimental data to provide additional insights into the characterization of Au2S nanocrystals.