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Issue 25, 2018
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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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Supplementary files

Article information


Submitted
26 Feb 2018
Accepted
23 May 2018
First published
25 May 2018

Nanoscale, 2018,10, 12093-12099
Article type
Paper
Author version available

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, 10, 12093
DOI: 10.1039/C8NR01611A

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