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RESEARCH PRODUCT
Gold/Isophorone Interaction Driven by Keto/Enol Tautomerization
Niklas NiliusHannu HäkkinenJanne NevalaitaKaroliina HonkalaChristian Stiehlersubject
010402 general chemistryPhotochemistry01 natural sciencesChemical reactionlaw.inventionchemistry.chemical_compoundlawketo-enol tautomerismgold compoundsMoleculePhysical and Theoretical Chemistryta116Isophoroneta114010405 organic chemistryKeto–enol tautomerismEnolTautomer0104 chemical sciencesSurfaces Coatings and FilmsElectronic Optical and Magnetic MaterialsisophoroneGeneral EnergychemistryDensity functional theoryScanning tunneling microscopedescription
The binding behavior of isophorone (C9H14O) to Au adatoms and clusters deposited on MgO/Ag(001) thin films is investigated by scanning tunneling microscopy (STM) and density functional theory (DFT). The STM data reveal the formation of various metal/organic complexes, ranging from Au1/isophorone pairs to larger Au aggregates with molecules bound to their perimeter. DFT calculations find the energetically preferred keto-isophorone to be unreactive toward gold, while the enol-tautomer readily binds to Au monomers and clusters. The interaction is governed by electrostatic forces between the hydroxyl group of the enol and negative excess charges residing on the ad-gold. The activation barrier between keto- and enol-isophorone is calculated to be 0.76 eV, rendering tautomerization feasible at room temperature. Our study provides evidence of an enol-driven chemical reaction of an organic molecule whose thermodynamic equilibrium lies far on the keto-side.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2016-09-19 | Journal of Physical Chemistry C |