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Single Ligand Exchange on an Au-Cu Bimetal Nanocluster and Mechanism

Abstract

An Au-Cu bimetallic nanocluster co-capped by selenolate and phosphine is obtained and its X-ray structure shows an icosahedral Au13 kernel surrounded by three CuSe2PPh2Py motifs and one CuSe3 motif, formulated as [Au13Cu4(PPh2Py)3(SePh)9]. Interestingly, a single-ligand-exchange process is observed in the growth reaction, in which an [Au13Cu4(PPh2Py)4(SePh)8]+ intermediate is first formed, but a prolong reaction leads to one PPh2Py ligand being selectively replaced by a PhSe- ligand. DFT simulations reveal that both steric hindrance and bond dissociation energy have great effects on the single-ligand-exchange reaction as well as the thermodynamics, which helps to understand the mechanism of the ligand-exchange. Temperature-dependent UV-vis absorption and photoluminescence (PL) properties of the Au-Cu nanocluster imply that the optical properties are mainly contributed by the metal core. Femtosecond time-resolved pump-probe analysis maps out further details of the PL process.

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Publication details

The article was received on 26 Feb 2018, accepted on 23 May 2018 and first published on 25 May 2018


Article type: Paper
DOI: 10.1039/C8NR01611A
Citation: Nanoscale, 2018, Accepted Manuscript
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    Single Ligand Exchange on an Au-Cu Bimetal Nanocluster and Mechanism

    Y. Song, Y. Lv, M. Zhou, T. Luo, S. Zhao, N. L. Rosi, H. Yu, M. Zhu and R. Jin, Nanoscale, 2018, Accepted Manuscript , DOI: 10.1039/C8NR01611A

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