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 journalArticle

76 Citations (Scopus)

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.
LanguageEnglish
Pages229-233
Number of pages5
JournalNature Nanotechnology
Volume3
Issue number4
DOIs
Publication statusPublished - 30 Apr 2008

Fingerprint

Oxides
metal oxides
electron transfer
Metals
Electrons
transition metals
Transition metals
Substrates
electronics
Electronic properties
sulfites
molybdenum oxides
electrons
Magnetic storage
data storage
nanoclusters
Sulfites
Molybdenum
Nanoclusters
catalysis

Keywords

  • computational nanotechnology
  • electronic properties devices
  • structural properties

Cite this

Fleming, Christopher ; Long, De-Liang ; McMillan, Nicola ; Johnston, Jacqueline ; Bovet, Nicolas ; Dhanak, Vin ; Gadegaard, Nikolaj ; Kogerler, Paul ; Cronin, Leroy ; Kadodwala, Malcolm . / Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates. In: Nature Nanotechnology. 2008 ; Vol. 3, No. 4. pp. 229-233.
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Fleming, C, Long, D-L, McMillan, N, Johnston, J, Bovet, N, Dhanak, V, Gadegaard, N, Kogerler, P, Cronin, L & Kadodwala, M 2008, 'Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates' Nature Nanotechnology, vol. 3, no. 4, pp. 229-233. https://doi.org/10.1038/nnano.2008.66

Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates. / Fleming, Christopher; Long, De-Liang; McMillan, Nicola; Johnston, Jacqueline; Bovet, Nicolas ; Dhanak, Vin ; Gadegaard, Nikolaj; Kogerler, Paul; Cronin, Leroy; Kadodwala, Malcolm .

In: Nature Nanotechnology, Vol. 3, No. 4, 30.04.2008, p. 229-233.

Research output: Contribution to journalArticle

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AU - Dhanak, Vin

AU - Gadegaard, Nikolaj

AU - Kogerler, Paul

AU - Cronin, Leroy

AU - Kadodwala, Malcolm

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AB - 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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