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Single-ligand exchange on an Au–Cu bimetal nanocluster and mechanism

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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 prolonged 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 help 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.

Graphical abstract: Single-ligand exchange on an Au–Cu bimetal nanocluster and mechanism

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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, Advance Article
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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, Advance Article , DOI: 10.1039/C8NR01611A

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