Article abstract
Nature Nanotechnology 3, 289 - 233 (2008)
Published online: 30 March 2008 | doi:10.1038/nnano.2008.66
Subject Categories: Computational nanotechnology | Electronic properties and devices | Structural properties
Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates
Christopher Fleming1, De-Liang Long1, Nicola McMillan1, Jacqueline Johnston1,4, Nicolas Bovet1, Vin Dhanak2,3, Nikolaj Gadegaard4, Paul Kögerler5, Leroy Cronin1 & Malcolm Kadodwala1
Abstract
Transition metal oxides exhibit a rich collection of electronic properties and have many practical applications in areas such as catalysis and ultra-high-density magnetic data storage. Therefore the development of switchable molecular transition metal oxides has potential for the engineering of single-molecule devices and nanoscale electronics. At present, the electronic properties of transition metal oxides can only be tailored through the irreversible introduction of dopant ions, modifying the electronic structure by either injecting electrons or core holes. Here we show that a molybdenum(VI) oxide 'polyoxometalate' molecular nanocluster containing two embedded redox agents is activated by a metallic surface and can reversibly interconvert between two electronic states. Upon thermal activation two electrons are ejected from the active sulphite anions and delocalized over the metal oxide cluster cage, switching it from a fully oxidized state to a two-electron reduced state along with the concomitant formation of an S–S bonding interaction between the two sulphur centres inside the cluster shell.
- Department of Chemistry, The University of Glasgow, Glasgow G12 8QQ, UK
- Physics Department, University of Liverpool L69 3BX, UK
- CLRC Daresbury Laboratory, Warrington WA4 4AD, UK
- Department of Electronics and Electrical Engineering, University of Glasgow, Glasgow G12 8LT, UK
- Ames Laboratory and Department of Physics & Astronomy, Iowa State University, Ames, IA 50011, USA
Correspondence to: Malcolm Kadodwala1 e-mail: malcolmk@chem.gla.ac.uk
Correspondence to: Leroy Cronin1 e-mail: L.Cronin@chem.gla.ac.uk
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