Through-Bond versus Through-Space Coupling in Mixed-Valence Molecules: Observation of Electron Localization at the Single-Molecule Scale.
Scanning tunneling microscopy (STM) is used to study two dinuclear organometallic molecules, meta-Fe2 and para-Fe2, which have identical molecular formulas but differ in the geometry in which the metal centers are linked through a central phenyl ring. Both molecules show symmetric electron density w...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 3; pp. 1710 - 1715 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
1/25/2012
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=71498675&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 71498675 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 1/25/2012 vid: 134 iid: 3 pid: 997 pub: American Chemical Society artinfo: ui: 71498675 10.1021/ja208981y ppf: 1710 ppct: 5 formats: tig: atl: Through-Bond versus Through-Space Coupling in Mixed-Valence Molecules: Observation of Electron Localization at the Single-Molecule Scale. aug: au: Quardokus, Rebecca C. Yuhui Lu Wasio, Natalie A. Lent, Craig S. Justaud, Frederic Lapinte, Claude Kandel, S. Alex affil: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States Department of Engineering, University of Notre Dame, Notre Dame, Indiana 46556, United States Sciences Chimiques de Rennes, UMR 6226 CNRS−Université de Rennes I, 35042 Rennes Cedex, France su: Scanning tunneling microscopy Electron distribution Symmetry (Biology) Density functionals Oxidation Phenyl compounds Iron sug: subj: Scanning tunneling microscopy Electron distribution Symmetry (Biology) Density functionals Oxidation Phenyl compounds Iron ab: Scanning tunneling microscopy (STM) is used to study two dinuclear organometallic molecules, meta-Fe2 and para-Fe2, which have identical molecular formulas but differ in the geometry in which the metal centers are linked through a central phenyl ring. Both molecules show symmetric electron density when imaged with STM under ultrahigh-vacuum conditions at 77 K. Chemical oxidation of these molecules results in mixed-valence species, and STM images of mixed-valence meta-Fe2 show pronounced asymmetry in electronic state density, despite the structural symmetry of the molecule. In contrast, images of mixed-valence para-Fe2 show that the electronic state density remains symmetric. Images are compared to constrained density functional (CDFT) calculations and are consistent with full localization of charge for meta-Fe2 on to a single metal center, as compared with charge delocalization over both metal centers for para-Fe2. The conclusion is that electronic coupling between the two metal centers occurs through the bonds of the organic linker, and through-space coupling is less important. In addition, the observation that mixed-valence para-Fe2 is delocalized shows that electron localization in meta-Fe2 is not determined by interactions with the Au(111) substrate or the position of neighboring solvent molecules or counterion species. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
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