X-ray Absorption Spectroscopy of Phosphine-Capped Au Clusters

Author:

Sharma Shailendra K.12,Johannessen Bernt3ORCID,Golovko Vladimir B.1ORCID,Marshall Aaron T.2

Affiliation:

1. School of Physical and Chemical Sciences, MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Canterbury, Christchurch 8041, New Zealand

2. Department of Chemical and Process Engineering, MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Canterbury, Christchurch 8041, New Zealand

3. Australian Synchrotron, ANSTO, Clayton, VIC 3168, Australia

Abstract

The structural determination of ultrasmall clusters remains a challenge due to difficulties in crystallisation. Often the atomically precise clusters undergo structural change under the influence of the environment. X-ray absorption spectroscopy (XAS) can be an attractive tool to study the electronic and geometric properties of such clusters deposited onto various supports under in situ conditions. Herein, [Au6(dppp)4](NO3)2, [Au9(PPh3)8](NO3)3, [Au13(dppe)5Cl2]Cl3, and Au101(PPPh3)21Cl5 clusters were studied using XAS. The clusters exhibited distinct features compared to bulk gold. XANES results show a systematic increase in the absorption edge energy and white line intensity, with a decrease in cluster nuclearity. The EXAFS of clusters are sensitive to nuclearity and ligands and were fitted with their known crystal structures. This study advances the understanding of the phosphine-ligated metal clusters relevant to practical applications in catalysis and sensing.

Funder

Australian Synchrotron, part of ANSTO

University of Canterbury

Publisher

MDPI AG

Subject

Inorganic Chemistry

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