Simple Approach toward N-Heterocyclic Carbene-Protected Gold Nanoclusters

Little advance has been made toward developing alternative bottom-up synthetic strategies for N-heterocyclic carbene (NHC)-stabilized gold nanoclusters, although this unique class of nanomaterials has exhibited exciting properties. We report in this work a simple and straightforward approach toward NHC-ligated gold nanoclusters by using imidazolium salts rather than free carbenes or NHC-coordinated gold complexes (NHC-Au-X, X is counterions) as precursors. Illustrated here is a one-pot and one-step preparation of an NHC-stabilized Au₁₃Br₄ cluster that features a distinct molecular formula, surface motifs, and assembling modes via chemical reduction of dpaAu, NaOMe, and ^FNHC^Bn·HBr by NaBH₄ (Hdpa is dipyridylamine; ^FNHC^Bn·HBr is 1,3-dibenzyl-5,6-difluoro-1H-benzo[d]imidazole-3-ium bromide). In situ UV-vis and NMR studies have elucidated the base-assisted formation of NHCs from imidazolium salts for the protection of the metal core. This work not only reports a new NHC-ligated superatom that completes the Au₁₃ library, thus facilitating structure-property studies, but also opens the door to explore underlying analogues in a facile and reasonable way.