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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Rhodium-silver superatomic nanoclusters stabilized by diselenophosphate ligands
Tzu-Hao Chiu1, Michael N Pillay1, Samia Kahlal2
1Department of Chemistry, National Dong Hwa University, Hualien, 97401, Taiwan, Republic of China. chenwei@gms.ndhu.edu.tw.
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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