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Hetero-biicosahedral [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ nanocluster: selective synthesis and optical and electrochemical properties

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Abstract

A recent study implied that a hetero-biicosahedral 25-atom cluster composed of two kinds of icosahedral 13-atom clusters could serve as a molecular rectifier and dipole material. However, no hetero-biicosahedral 25-atom clusters containing three types of ligands, in this case, phosphines, halogens, and thiolates, have been reported. In this study, we selectively synthesized [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]Cl (Au = gold, Pd = palladium, PPh3 = triphenylphosphine, SC2H4Ph = phenylethanethiolate, Cl = chloride), in which one Au was replaced with a Pd. The single-crystal X-ray structural analysis demonstrated that [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]Cl was a hetero-biicosahedral 25-atom cluster in which the central atom of one icosahedral Au13 core was replaced by a Pd atom. Optical absorption spectroscopy suggested that the electronic structure of each individual icosahedral 13-atom core in [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ was reasonably well maintained, similar to the case of [Au25(PPh3)10(SC2H4Ph)5Cl2]2+. Density functional theory calculation revealed that the peak splitting in the region below 2.2 eV of the optical absorption spectrum of [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ is due to the splitting of HOMOs and also suggested that this cluster has dipole moment. Electrochemical measurements showed that [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ was relatively stable to reduction. These results are expected to contribute to the development of molecular rectifiers and dipole materials based on hetero-biicosahedral 25-atom clusters.

Graphical abstract: Hetero-biicosahedral [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ nanocluster: selective synthesis and optical and electrochemical properties

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Publication details

The article was received on 20 May 2018, accepted on 10 Aug 2018 and first published on 10 Aug 2018


Article type: Paper
DOI: 10.1039/C8NR04078H
Citation: Nanoscale, 2018, Advance Article
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    Hetero-biicosahedral [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ nanocluster: selective synthesis and optical and electrochemical properties

    L. V. Nair, S. Hossain, S. Takagi, Y. Imai, G. Hu, S. Wakayama, B. Kumar, W. Kurashige, D. Jiang and Y. Negishi, Nanoscale, 2018, Advance Article , DOI: 10.1039/C8NR04078H

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