Cu(14) Cluster with Partial Cu(0) Character: Difference in Electronic Structure from Isostructural Silver Analog

具有部分 Cu(0) 特征的 Cu(14) 簇:与同构银类似物的电子结构差异

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Abstract

An atom-precise Cu(0)-containing copper cluster, Cu(14)(C(2)B(10)H(10)S(2))(6)(CH(3)CN)(8) (abbreviated as Cu(14)-8CH(3)CN) 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. Cu(14)-8CH(3)CN is the only copper cluster that has a virtually identical silver structural analog, i.e., Ag(14)(C(2)B(10)H(10)S(2))(6)(CH(3)CN)(8) (hereafter as Ag(14)-8CH(3)CN). Nevertheless, density functional theory calculations reveal that the electronic structure of Cu(14)-8CH(3)CN differs significantly from the superatom electronic configuration of Ag(14)-8CH(3)CN. Moreover, Cu(14)-8CH(3)CN shows room-temperature luminescence and good electrocatalytic activities in the ethanol oxidation reaction and detection of H(2)O(2). 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.

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