4.8 Article

Solvent-mediated precipitating synthesis and optical properties of polyhydrido Cu13 nanoclusters with four vertex-sharing tetrahedrons

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CHEMICAL SCIENCE
卷 14, 期 4, 页码 994-1002

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d2sc06099j

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A novel solvent-mediated precipitating synthesis (SMPS) method was used to prepare high purity and high yield Cu13 nanoclusters, revealing their unique structure and optical properties.
Structurally defined metal nanoclusters facilitate mechanism studies and promote functional applications. However, precisely constructing copper nanoclusters remains a long-standing challenge in nanoscience. Developing new efficient synthetic strategies for Cu nanoclusters is highly desirable. Here, we propose a solvent-mediated precipitating synthesis (SMPS) to prepare Cu13H10(SR)(3)(PPh3)(7) nanoclusters (H-SR = 2-chloro-4-fluorobenzenethiol). The obtained Cu-13 nanoclusters are high purity and high yield (39.5%, based on Cu atom), proving the superiority of the SMPS method. The Cu-13 nanoclusters were comprehensively studied via a series of characterizations. Single crystal X-ray crystallography shows that the Cu-13 nanoclusters contain a threefold symmetry axis and the Cu-13 kernel is protected by a monolayer of ligands, including PPh3 and thiolates. Unprecedentedly, the aesthetic Cu-13 kernel is composed of four vertex-sharing tetrahedrons, rather than the common icosahedral or cuboctahedral M-13. The intramolecular pi MIDLINE HORIZONTAL ELLIPSIS pi interactions between thiolates and PPh3 on the surface contribute to the stable configuration. Furthermore, electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) revealed the existence of ten hydrides, including four types of hydrides. Density functional theory (DFT) calculations without simplifying the ligands simulated the location of the 10 hydrides in the crystal structure. Additionally, the steady-state ultraviolet-visible absorption and fluorescence spectra of the Cu-13 nanoclusters exhibit unique optical absorbance and photoluminescence. The ultrafast relaxation dynamics were also studied via transient absorption spectroscopy, and the three decay components are attributed to the relaxation pathways of internal conversion, structural relaxation and radiative relaxation. This work provides not only a novel SMPS strategy to efficiently synthesize Cu-13 nanoclusters, but also a better insight into the structural characteristics and optical properties of the Cu nanoclusters.

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