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Halogen effects on the electronic and optical properties of Au₁₃ nanoclusters.

ABSTRACT: We report an experimental and theoretical investigation of the electronic and optical properties of a series of icosahedral Au₁₃ nanoclusters, protected using different halogen ligands (Cl, Br, and I), as well as 1,2-bis(diphenylphosphino)ethane (dppe) ligands. All three clusters are comprised of the same Au₁₃ kernel with two halogens coordinated to the poles of the icosahedral cluster along with five dppe ligands. UV-vis absorption spectra indicate a systematic red shift from Cl to Br to I, as well as a sudden enhancement of the second excitonic peak for the I-coordinated cluster. Density functional theory (DFT) calculations suggest that all clusters possess a wide HOMO-LUMO energy gap of ∼1.79 eV and are used to assign the first two excitonic bands. Frontier orbital analyses reveal several HOMO → LUMO transitions involving halogen-to-metal charge transfers. For the I-coordinated cluster, more complicated I-to-metal charge transfers give rise to different excitation features observed experimentally. The current findings show that halogen ligands play important roles in the electronic structures of gold clusters and can be utilized to tune the optical properties of the clusters.

SUBMITTER: Gao ZH

PROVIDER: S-EPMC9419307 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

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Halogen effects on the electronic and optical properties of Au13 nanoclusters.

Gao Ze-Hua ZH Dong Jia J Zhang Qian-Fan QF Wang Lai-Sheng LS

Nanoscale advances 20200831 10

We report an experimental and theoretical investigation of the electronic and optical properties of a series of icosahedral Au13 nanoclusters, protected using different halogen ligands (Cl, Br, and I), as well as 1,2-bis(diphenylphosphino)ethane (dppe) ligands. All three clusters are comprised of the same Au13 kernel with two halogens coordinated to the poles of the icosahedral cluster along with five dppe ligands. UV-vis absorption spectra indicate a systematic red shift f ...[more]

PMID: 36132903

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Project description: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 Cu13 nanoclusters are high purity and high yield (39.5%, based on Cu atom), proving the superiority of the SMPS method. The Cu13 nanoclusters were comprehensively studied via a series of characterizations. Single crystal X-ray crystallography shows that the Cu13 nanoclusters contain a threefold symmetry axis and the Cu13 kernel is protected by a monolayer of ligands, including PPh3 and thiolates. Unprecedentedly, the aesthetic Cu13 kernel is composed of four vertex-sharing tetrahedrons, rather than the common icosahedral or cuboctahedral M13. The intramolecular π⋯π 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 Cu13 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 Cu13 nanoclusters, but also a better insight into the structural characteristics and optical properties of the Cu nanoclusters.

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Halogen effects on the electronic and optical properties of Au₁₃ nanoclusters.

Publications

Halogen effects on the electronic and optical properties of Au<sub>13</sub> nanoclusters.

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