Total Structure, Structural Transformation and Catalytic Hydrogenation of [Cu 41 (SC 6 H 3 F 2 ) 15 Cl 3 (P(PhF) 3 ) 6 (H) 25 ] 2- Constructed from Twisted Cu 13 Units

Herein, a remarkable achievement in the synthesis and characterization of an atomically precise copper-hydride nanocluster, [Cu (SC H F ) Cl (P(PhF) ) (H) ] via a mild one-pot reaction is presented. Through X-ray crystallography analysis, it is revealed that [Cu (SC H F ) Cl (P(PhF) ) (H) ] exhibits a unique shell-core-shell structure. The inner Cu kernel is composed of three twisted Cu units, connected through Cu face sharing. Surrounding the metal core, two Cu metal shells, resembling a protective sandwich structure are observed. This arrangement, along with intracluster π···π interactions and intercluster C─H···F─C interactions, contributes to the enhanced stability of [Cu (SC H F ) Cl (P(PhF) ) (H) ] . The presence, number, and location of hydrides within the nanocluster are established through a combination of experimental and density functional theory investigations. Notably, the addition of a phosphine ligand triggers a fascinating nanocluster-to-nanocluster transformation in [Cu (SC H F ) Cl (P(PhF) ) (H) ] , resulting in the generation of two nanoclusters, [Cu (SC H F ) (PPh ) H ] and [Cu (SC H F ) (P(PhF) ) H ] . Furthermore, it is demonstrated that [Cu (SC H F ) Cl (P(PhF) ) (H) ] exhibits catalytic activity in the hydrogenation of nitroarenes. This intriguing nanocluster provides a unique opportunity to explore the assembly of M units, similar to other coinage metal nanoclusters, and investigate the nanocluster-to-nanocluster transformation in phosphine and thiol ligand co-protected copper nanoclusters.