N-Heterocyclic Carbene Ligands for Au Nanocrystal Stabilization and Three-Dimensional Self-Assembly

[Image: see text] N-Heterocyclic carbenes (NHCs) have emerged as a new class of ligands for materials chemistry that appears particularly relevant for the stabilization and functionalization of metal nanoparticles (NPs). The particular properties and high synthetic flexibility of NHCs make them highly attractive tools for the development of new (nano)materials and the fundamental study of their properties. The relationships between the NHC structure and NP structure/properties, including physical, biological, and self-assembly properties, remain largely unknown. In the past decade, many efforts have been made to gain more fundamental understanding in this area. In this feature article, we present our contribution in this field focusing on the formation of NHC-coated Au nanocrystals (NCs), their stability, and their ability to self-assemble into 3D crystalline structures called supracrystals. First, the formation of NHC-stabilized Au NCs is discussed by comparing different NHC structures, NHC-based Au precursors, and synthesis methods. This study shows the major role of the NHC structure in obtaining both stable NHC-coated Au NCs and narrow size distributions. In a second part, a comparative study of the oxygen resistance of NHC- and thiol-coated NCs is presented, demonstrating the enhanced stability of NHC-coated Au NCs to oxygen-based treatments. Finally, the self-assembly of NHC-coated Au NCs into 3D Au superlattices is presented. The formation of large organized domains of several micrometers is described from the design of NHCs tailored with long alkyl chains. In these different contexts, efforts have been made to gain a more in-depth understanding of the behavior of NHC ligands at the surface of NCs. These results show that the NHC-based approach to nanomaterials has many assets for opening a new research area in the supracrystal world.