Total Structure, Structural Transformation and Catalytic Hydrogenation of [Cu<sub>41</sub>(SC<sub>6</sub>H<sub>3</sub>F<sub>2</sub>)<sub>15</sub>Cl<sub>3</sub>(P(PhF)<sub>3</sub>)<sub>6</sub>(H)<sub>25</sub>]<sup>2−</sup> Constructed from Twisted Cu<sub>13</sub> Units
Huimin Zhou, Tengfei Duan, Zidong Lin, Tao Yang, Huijuan Deng, Shan Jin, Yong Pei, Manzhou Zhu
Abstract
Abstract 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.