Cu14 Cluster with Partial Cu(0) Character: Difference in Electronic Structure from Isostructural Silver Analog

Abstract

Abstract An atom‐precise Cu0‐containing copper cluster, Cu14(C2B10H10S2)6(CH3CN)8 (abbreviated as Cu14‐8CH3CN) is reported, which is synthesized via a simultaneous reduction strategy and fully characterized by single‐crystal X‐ray diffraction, ESI‐TOF‐MS, and X‐ray photoelectron spectroscopy. Cu14‐8CH3CN is the only copper cluster that has a virtually identical silver structural analog, i.e., Ag14(C2B10H10S2)6(CH3CN)8 (hereafter as Ag14‐8CH3CN). Nevertheless, density functional theory calculations reveal that the electronic structure of Cu14‐8CH3CN differs significantly from the superatom electronic configuration of Ag14‐8CH3CN. Moreover, Cu14‐8CH3CN shows room‐temperature luminescence and good electrocatalytic activities in the ethanol oxidation reaction and detection of H2O2. This pair of unprecedented analogous molecular nanoscale systems offer an ideal platform to investigate the fundamental differences between copper and silver in terms of catalytic activity and optical properties.

Keywords

• analogs
• Cu clusters
• Cu(0) character
• electronic structure
• luminescence