Abstract: Controlling the generation of organized 3D assemblies of individual nanocrystals, called supracrystals, as well as their properties, is an important challenge for the design of new materials in which the coating agent plays a major role. We present herein a new generation of structured fcc Au supracrystals made of N-heterocyclic carbene (NHC)-coated Au nanocrystals. The 3D assemblies were achieved by using benzimidazole-derived NHCs tailored with long alkyl chains at different positions...