Mechanochemical synthesis of silver(I)-N-heterocyclic carbene assemblies

Organometallic supramolecular assemblies containing N-heterocyclic carbene (NHC) ligands linked via metal–carbon bonding have attracted attention in recent years because of their functional applications in biochemistry, catalysis, and materials science. However, most methods currently used to construct poly-NHC metallosupramolecular assemblies are solution-based methods that suffer from cumbersome procedures and the need for harsh conditions, which greatly limits the research in this area. Herein, a general, efficient, and simplified mechanochemical synthesis protocol was developed and was used to construct more than 70 diverse poly-NHC silver(I) assemblies (e.g., metallacycles, metallocages, and interlocked assemblies), thus overcoming the shortcomings of the solution-based methods. Highly selective narcissistic or social self-sorting was observed during this solid-state mechanochemical complexation process. In addition, this new method, which has the advantages of low energy consumption, high yields, a short reaction time, and minimal solvent waste, facilitates the synthesis of poly-NHC silver(I) assemblies and allows the subsequent large-scale synthesis and functional exploration of such architectures.