Issue 46, 2006
From the journal:

Physical Chemistry Chemical Physics

A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping†

Michael Waltera  and  Hannu Häkkinen*a  

* Corresponding authors

a Department of Physics, Nanoscience Center (NSC), University of Jyväskylä, Finland
E-mail: hannu.hakkinen@phys.jyu.fi
Fax: +358 14 260 4756
Tel: +358 14 260 4719

Abstract

We show, via density functional theory calculations, that dianionic Au162− cluster has a stable, hollow, Td symmetric cage structure, stabilized by 18 delocalized valence electrons. The cage maintains its robust geometry, with a minor Jahn–Teller deformation, over several charge states (q = −1,0,+1), forming spin doublet, triplet and quadruplet states according to the Hund’s rules. Endohedral doping of the Au16 cage by Al or Si yields a geometrically robust, tuneable oxidation and reduction agent. Si@Au16 is a magic species with 20 delocalized electrons. We calculate a significant binding energy for the anionic Si@Au16/O2− complex and show that the adsorbed O2 is activated to a superoxo-species, a result which is at variance with the experimentally well-documented inertness of Au16− anion towards oxygen uptake.

Graphical abstract: A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping

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Article information

DOI
https://doi.org/10.1039/B612221C
Article type
Communication
Submitted
24 Aug 2006
Accepted
06 Oct 2006
First published
18 Oct 2006

Phys. Chem. Chem. Phys., 2006,8, 5407-5411

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A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping

M. Walter and H. Häkkinen, Phys. Chem. Chem. Phys., 2006, 8, 5407 DOI: 10.1039/B612221C

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