Dataset Information

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

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.

SUBMITTER: Li YL

PROVIDER: S-EPMC6755520 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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

Li Yan-Ling YL Wang Jie J Luo Peng P Ma Xiao-Hong XH Dong Xi-Yan XY Wang Zhao-Yang ZY Du Chen-Xia CX Zang Shuang-Quan SQ Mak Thomas C W TCW

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20190726 18

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 si ...[more]

PMID: 31559130

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Project description:The experimental electron-density distribution in two isostructural complexes, tetrakis(?2-acetato)diaquadicopper(II) [H2OCu(ac)2Cu(ac)2H2O] and tetrakis(?2-acetato)diaquadichromium(II) [H2OCr(ac)2Cr(ac)2H2O], has been studied and compared. The experimental electron density distribution in two isostructural and isomorphous complexes, tetrakis(?2-acetato)diaquadicopper(II) [H2OCu(ac)2Cu(ac)2H2O] (I) and tetrakis(?2-acetato)diaquadichromium(II), [H2OCr(ac)2Cr(ac)2H2O] (II), has been obtained from high-resolution X-ray diffraction data in order to shed light on the bonding properties in the compounds studied. It has been shown that from accurate X-ray data it is possible to discuss the bonding capability of the metal atom (Cu/Cr) and the ligands in these complexes. A comparison of results obtained from averaged and non-averaged X-ray data demonstrates that using the non-averaged data and introducing an anisotropic correction for secondary extinction errors provides a more detailed distribution of the electron density in the area of the metal atoms. In both complexes studied, the bonding of the acetate oxygen atom to the central metal atom is significantly affected by the formation of hydrogen bonds. The electron density and its Laplacian at the bond critical point of metal–oxygen coordination bonds for those oxygen atoms not involved in the intermolecular hydrogen bonds are approximately 10% larger compared with the case when oxygen atoms take part in hydrogen bonds with the neighboring water molecules. It is shown that metal–oxygen bonds in a quasi-equatorial plane are typical coordination bonds and differ significantly from the apical metal–oxygen bond. Metal–metal interaction with a small positive value of the electron density Laplacian at this bond critical point is mainly of electrostatic character. The metal–metal interaction is definitely not a bond according to the classical definition. Based on a search of the Cambridge Structural Database, it can be argued that there are four typical coordination bonds in the [CuO6] chromophore, similar to the four Cu—O coordination bonds in the basal plane of the CuO5 pyramid in one of the complexes under study.

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Dataset Information

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

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Cu<sub>14</sub> Cluster with Partial Cu(0) Character: Difference in Electronic Structure from Isostructural Silver Analog.

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