0000000000465387

AUTHOR

Barbara Kirchner

0000-0001-8843-7132

Interfacial Domain Formation Enhances Electrochemical Synthesis.

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 bo…

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Substituent effects on axle binding in amide pseudorotaxanes: comparison of NMR titration and ITC data with DFT calculations

The binding behaviour of differently substituted diamide axle molecules to Hunter/Vögtle tetralactam macrocycles was studied with a combination of NMR titration, isothermal titration calorimetry (ITC) experiments and calculations employing density functional theory (DFT), along with dispersion-corrected exchange-correlation functionals. Guests with alkyl or alkenyl chains attached to the diamide carbonyl groups have a significantly higher binding affinity to the macrocycle than guests with benzoyl amides and their substituted analogues. While the binding of the benzoyl and alkenyl substituted axles is enthalpically driven, the alkyl-substituted guest binds mainly because of a positive bindi…

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The Catalytic Effect of Fluoroalcohol Mixtures Depends on Domain Formation

In the present contribution, we investigated catalytically active mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and aqueous H2O2 by molecular dynamics simulations. It is clearly observable that the HFIP molecule strongly binds to the H2O2, which is necessary for the desired catalytic reaction to occur. Upon the addition of the substrate cyclooctene to the solution, this interaction is enhanced, which suggests that the catalytic activity is increased by the presence of the hydrocarbon. We could clearly observe the microheterogeneous structure of the mixture, which is the result of the separation of the hydroxyl groups, water, and H2O2 from the fluorinated alkyl moiety in the form of l…

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