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

TitleReversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates
Publication TypeJournal Article
Year of Publication2008
AuthorsFleming C, Long DL, McMillan N, Johnston J, Bovet N, Dhanak V, Gadegaard N, Kogerler P, Cronin L, Kadodwala M
Journal TitleNature Nanotechnology
Volume3
Pages229-233
Date PublishedApr
Type of ArticleArticle
ISBN Number1748-3387
Accession NumberISI:000254744300015
Keywordsclusters, HYBRID, molecules, POLYOXOMETALATE, surface, TRANSITIONS
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.

DOI10.1038/nnano.2008.66
Alternate JournalNat. Nanotechnol.