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 41 (SC 6 H 3 F 2 ) 15 Cl 3 (P(PhF) 3 ) 6 (H) 25 ] 2- via a mild one-pot reaction is presented. Through X-ray crystallography analysis, it is revealed that [Cu 41 (SC 6 H 3 F 2 ) 15 Cl 3 (P(PhF) 3 ) 6 (H) 25 ] 2- exhibits a unique shell-core-shell structure. The inner Cu 29 kernel is composed of three twisted Cu 13 units, connected through Cu 4 face sharing. Surrounding the metal core, two Cu 6 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 41 (SC 6 H 3 F 2 ) 15 Cl 3 (P(PhF) 3 ) 6 (H) 25 ] 2- . 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 41 (SC 6 H 3 F 2 ) 15 Cl 3 (P(PhF) 3 ) 6 (H) 25 ] 2- , resulting in the generation of two nanoclusters, [Cu 14 (SC 6 H 3 F 2 ) 3 (PPh 3 ) 8 H 10 ] + and [Cu 13 (SC 6 H 3 F 2 ) 3 (P(PhF) 3 ) 7 H 10 ] 0 . Furthermore, it is demonstrated that [Cu 41 (SC 6 H 3 F 2 ) 15 Cl 3 (P(PhF) 3 ) 6 (H) 25 ] 2- exhibits catalytic activity in the hydrogenation of nitroarenes. This intriguing nanocluster provides a unique opportunity to explore the assembly of M 13 units, similar to other coinage metal nanoclusters, and investigate the nanocluster-to-nanocluster transformation in phosphine and thiol ligand co-protected copper nanoclusters.