6533b820fe1ef96bd12799e8
RESEARCH PRODUCT
Interfacial Domain Formation Enhances Electrochemical Synthesis.
Barbara GleedeOldamur HollóczkiRoberto MacchieraldoBarbara KirchnerSiegfried R. Waldvogelsubject
Materials science010405 organic chemistryHydrogen bondAryl010402 general chemistryElectrochemistry01 natural sciences0104 chemical sciencesCatalysisSolventMolecular dynamicschemistry.chemical_compoundchemistryChemical physicsGeneral Materials ScienceDensity functional theoryPhysical and Theoretical ChemistrySelectivitydescription
The electroorganic C,C coupling of phenols to other aryl components is controlled by the fluoroalcohol-alcohol mixture solvents. Classical molecular dynamics and static density functional theory reveal that both kinds of solvents interact with the substrates, influencing the electronic structure of a phenoxyl radical intermediate in a cooperative manner to achieve maximal efficiency and selectivity. Simulations of the electrolyte-electrode interface showed that the substrates adsorb on the diamond surface in such a way that the repulsive fluorous-lipophilic interactions can be minimized and the attractive lipophilic-lipophilic interplay can be maximized, whereas the advantageous hydrogen bonding with the solvent can be retained. Accordingly, the solvent induces efficiency through the interaction of hydrogen bonding and the structure that controls the mesoscopic separation in these fluids. Since these findings are not specific to electrochemistry, by extending this principle to other heterogeneous processes, e.g., catalysis, their rate, yield, and selectivity can be potentially increased as well.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2019-02-26 | The journal of physical chemistry letters |