Guiding the High-Yield Synthesis of NHC-Ligated Gold Nanoclusters by 19F NMR Spectroscopy

Optimizing the synthesis of atomically precise metal nanoclusters by virtue of molecular tools is highly desirable but quite challenging. Herein we report how ¹⁹F NMR spectroscopy can be used to guide the high-yield synthesis of N-heterocyclic carbene (NHC)-stabilized gold nanoclusters. In spite of little difference, ¹⁹F NMR signals of fluoro-incorporated NHCs (^FNHC) are highly sensitive to the tiny change in their surrounding chemical environments with different N-substituents, metals, or anions, thus providing a convenient strategy to discriminate species in reaction mixtures. By using ¹⁹F NMR, we first disclosed that the one-pot reduction of ^FNHC-Au-X (X is halide) yields multiple compounds, including cluster compounds and also a large amount of highly stable [Au(^FNHC)₂]⁺ byproduct. The detailed quantitative ¹⁹F NMR analyses over the reductive synthesis of NHC-stabilized Au nanoclusters reveal that the formation of the di-NHC complex is deleterious to the high-yield synthesis of NHC-stabilized Au nanoclusters. With the understanding, the reaction kinetic was then slowed by controlling the reduction rate to achieve the high yield of a [Au₂₄(^FNHC)₁₄X₂H₃]³⁺ nanocluster with a unique structure. The strategy demonstrated in this work is expected to provide an effective tool to guide the high-yield synthesis of organic ligand-stabilized metal nanoclusters.