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.
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Acknowledgements
The authors would like to thank the Leverhulme Trust (London), the Royal Society, the University of Glasgow, WestCHEM and the Engineering and Physical Sciences Research Council (UK) for funding.
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L.C. and M.K. conceived and designed the experiments, D.L. synthesized the clusters and N.G., N.M. and J.J. prepared the samples for the photoemission studies. C.F. and J.J. performed the experiments, M.K., C.F. and J.J. analysed the photoemission data, and N.B. and V.D. helped with the synchrotron experiments. P.K. performed the theoretical calculations. M.K. and L.C. co-wrote the paper.
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Fleming, C., Long, DL., McMillan, N. et al. Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates. Nature Nanotech 3, 229–233 (2008). https://doi.org/10.1038/nnano.2008.66
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DOI: https://doi.org/10.1038/nnano.2008.66
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