Exposing the Dynamics and Energetics of the N-Heterocyclic Carbene–Nanocrystal Interface
2016
Lu, Haipeng | Zhou, Zhaohui | Prezhdo, Oleg V. | Brutchey, Richard L.
N-Heterocyclic carbenes (NHCs) are becoming increasingly popular ligand frameworks for nanocrystal surfaces; however, as of yet the nature of the NHC–nanocrystal interface remains unexplored across different material types. Here we report a facile synthetic route to NHC-stabilized metal and metal chalcogenide nanocrystals. It was observed that NHC–Ag nanocrystals are colloidally stable, but much less so than the corresponding NHC–Ag₂E analogues. Comprehensive NMR studies suggest a dynamic NHC–nanocrystal interface for both NHC–Ag and NHC–Ag₂S; however, density functional theory calculations reveal a much stronger binding affinity of the NHC ligands to Ag₂S compared with Ag nanocrystals, which explains the superior colloidal stability of the metal chalcogenides. This offers new insight into the surface chemistry of neutral L-type carbenes in colloidal nanocrystal chemistry.
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