Hierarchical Assembly of High-Nuclearity Copper(I) Alkynide Nanoclusters: Highly Effective CO Electroreduction Catalyst toward Hydrocarbons.

The pursuit of precision in the engineering of metal nanoparticle assemblies has long fascinated scientists, but achieving atomic-level accuracy continues to pose a significant challenge. This research sheds light on the hierarchical assembly processes of two high-nuclearity Cu(I) nanoclusters (NCs). By employing a multiligand cooperative stabilization strategy, we have isolated a series of thiacalix[4]arene (TC4A)/alkynyl coprotected Cu(I) NCs (, where = , , , ). These NCs are intricately coassembled from the fundamental building units of {Cu(TC4A)} and alkynyl-stabilized CuL in various ratios. By capturing active anion templates such as O, Cl, or C that are generated in situ, we have further explored the secondary structural self-assembly of these clusters. serves as a secondary assembly module for constructing and , which exhibit the highest nuclearity reported to date among Cu(I) NCs encased in macrocyclic ligands. Notably, demonstrates an impressive Faradaic efficiency of 62.01% for hydrocarbons at -1.57 V vs RHE during CO electroreduction, with 34.03% for CH and 27.98% for CH. This performance establishes it as an exceptionally rare, large, atomically precise metal NC (nuclearity >30) capable of catalyzing the formation of highly electro-reduced hydrocarbon products. Our research has introduced a new approach for constructing high-nuclearity Cu(I) NCs through a hierarchical assembly method and investigating their potential in the electrocatalytic transformation of CO into hydrocarbons.