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

Christopher Fleming, De-Liang Long, Nicola McMillan, Jacqueline Johnston, Nicolas Bovet, Vin Dhanak, Nikolaj Gadegaard, Paul Kogerler, Leroy Cronin, Malcolm Kadodwala

Research output: Contribution to journalArticlepeer-review

87 Citations (Scopus)


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.
Original languageEnglish
Pages (from-to)229-233
Number of pages5
JournalNature Nanotechnology
Issue number4
Publication statusPublished - 30 Apr 2008


  • computational nanotechnology
  • electronic properties devices
  • structural properties


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