Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates

Fleming, C., Long, D. L. , McMillan, N., Johnston, J., Bovet, N., Dhanak, V., Gadegaard, N. , Kogerler, P., Cronin, L. and Kadodwala, M. (2008) Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates. Nature Nanotechnology, 3(4), pp. 229-233. (doi:10.1038/nnano.2008.66)

Fleming, C., Long, D. L. , McMillan, N., Johnston, J., Bovet, N., Dhanak, V., Gadegaard, N. , Kogerler, P., Cronin, L. and Kadodwala, M. (2008) Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates. Nature Nanotechnology, 3(4), pp. 229-233. (doi:10.1038/nnano.2008.66)

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Publisher's URL: http://dx.doi.org/10.1038/nnano.2008.66

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.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Long, Dr De Liang and Cronin, Professor Leroy and Gadegaard, Professor Nikolaj and Kadodwala, Professor Malcolm
Authors: Fleming, C., Long, D. L., McMillan, N., Johnston, J., Bovet, N., Dhanak, V., Gadegaard, N., Kogerler, P., Cronin, L., and Kadodwala, M.
College/School:College of Science and Engineering > School of Chemistry
College of Science and Engineering > School of Engineering > Biomedical Engineering
Journal Name:Nature Nanotechnology
ISSN:1748-3387
ISSN (Online):1748-3395
Published Online:30 March 2008

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
400011Understanding and controlling the self assembly of nanoscale polyoxometalate clustersLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/C542819/1CHEM - CHEMISTRY