%0 Journal Article
%T Total Structure, Structural Transformation and Catalytic Hydrogenation of [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- Constructed from Twisted Cu13 Units.
%A Zhou H
%A Duan T
%A Lin Z
%A Yang T
%A Deng H
%A Jin S
%A Pei Y
%A Zhu M
%J Adv Sci (Weinh)
%V 11
%N 7
%D 2024 Feb 8
%M 38064120
%F 17.521
%R 10.1002/advs.202307085
%X Herein, a remarkable achievement in the synthesis and characterization of an atomically precise copper-hydride nanocluster, [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- via a mild one-pot reaction is presented. Through X-ray crystallography analysis, it is revealed that [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- exhibits a unique shell-core-shell structure. The inner Cu29 kernel is composed of three twisted Cu13 units, connected through Cu4 face sharing. Surrounding the metal core, two Cu6 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 [Cu41 (SC6 H3 F2 )15 Cl3 (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 [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- , resulting in the generation of two nanoclusters, [Cu14 (SC6 H3 F2 )3 (PPh3 )8 H10 ]+ and [Cu13 (SC6 H3 F2 )3 (P(PhF)3 )7 H10 ]0 . Furthermore, it is demonstrated that [Cu41 (SC6 H3 F2 )15 Cl3 (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 M13 units, similar to other coinage metal nanoclusters, and investigate the nanocluster-to-nanocluster transformation in phosphine and thiol ligand co-protected copper nanoclusters.