Rhodium–silver superatomic nanoclusters stabilized by diselenophosphate ligands†

IF 5.1 3区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Nanoscale Pub Date : 2025-05-14 DOI:10.1039/D5NR01190F

Tzu-Hao Chiu, Michael N. Pillay, Samia Kahlal, Jean-Yves Saillard and C. W. Liu

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Abstract

Ligand replacement is an efficient and high-yield synthesis method that is valuable in constructing multifunctional nanoclusters. We report the first Rh/Ag alloy nanoclusters stabilized by selenium-based ligands, namely [RhH₂Ag₁₉{Se₂P(OⁱPr)₂}₁₂] (1), [RhHAg₂₀{Se₂P(OⁱPr)₂}₁₂] (2), and [RhAg₂₁{Se₂P(OⁱPr)₂}₁₂] (3). These nanoclusters were comprehensively characterized by UV-vis spectroscopy, photoluminescence, ESI mass spectrometry, X-ray crystallography and DFT analysis. The metal cores of these three nanoclusters closely resemble their sulfur analogs, with the primary distinction lying in the location of the peripheral capping silver atoms due to the difference in the bite distances of the S- and Se-chelates. Compared to their sulfur analogs, a significant red shift was observed in the absorption spectra of 1, 2, and 3, but a blue shift in the photoluminescence spectra.

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二磷酸配体稳定的铑银超原子纳米团簇

配体置换是一种高效、高产的合成方法，在构建多功能纳米团簇中具有重要的应用价值。我们在下面报道了由硒基配体稳定的第一个Rh/Ag合金纳米团簇，即[RhH2Ag19{Se2P(OiPr)2}12] (1), [RhHAg20{Se2P(OiPr)2}12](2)和[RhAg21{Se2P(OiPr)2}12](3)。通过紫外可见光谱、光致发光、ESI质谱、x射线晶体学和DFT分析对这些纳米团簇进行了全面表征。这三种纳米簇的金属核与它们的硫类似物非常相似，主要区别在于外围覆盖银原子的位置，这是由于S-螯合物和se螯合物的咬距不同。与它们的硫类似物相比，在1、2和3的吸收光谱中观察到明显的红移，但在光致发光光谱中观察到蓝移。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Nanoscale CHEMISTRY, MULTIDISCIPLINARY-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

12.10

自引率

3.00%

发文量

1628

审稿时长

1.6 months

期刊介绍： Nanoscale is a high-impact international journal, publishing high-quality research across nanoscience and nanotechnology. Nanoscale publishes a full mix of research articles on experimental and theoretical work, including reviews, communications, and full papers.Highly interdisciplinary, this journal appeals to scientists, researchers and professionals interested in nanoscience and nanotechnology, quantum materials and quantum technology, including the areas of physics, chemistry, biology, medicine, materials, energy/environment, information technology, detection science, healthcare and drug discovery, and electronics.