The quest for determining one-electron redox potentials of azulene-1-carbonitriles by calculation

TY - JOUR

T1 - The quest for determining one-electron redox potentials of azulene-1-carbonitriles by calculation

AU - Ree, Nicolai

AU - Andersen, Cecilie Lindholm

AU - Kilde, Martin Drøhse

AU - Hammerich, Ole

AU - Nielsen, Mogens Brøndsted

AU - Mikkelsen, Kurt Valentin

PY - 2018

Y1 - 2018

N2 - Electrochemical processes drive many chemical and biochemical reactions. Theoretical methods to accurately predict redox potentials are therefore crucial for understanding these reactions and designing new chemical species with desired properties. We have investigated a theoretical methodology using electronic structure methods based on density functional theory and continuum solvation models. These methods have been validated with linear correlation plots comparing theoretical and experimental results for the redox properties of a series of azulene derivatives. The results showed excellent correlations despite only minor structural variations of the azulenes, which support this rather simple theoretical methodology for determining redox potentials of organic molecules. Furthermore, we have estimated the absolute redox potential of the ferrocene/ferrocenium redox couple to be 4.8 ± 0.1 V in dichloromethane, which is slightly lower than previous estimates.

AB - Electrochemical processes drive many chemical and biochemical reactions. Theoretical methods to accurately predict redox potentials are therefore crucial for understanding these reactions and designing new chemical species with desired properties. We have investigated a theoretical methodology using electronic structure methods based on density functional theory and continuum solvation models. These methods have been validated with linear correlation plots comparing theoretical and experimental results for the redox properties of a series of azulene derivatives. The results showed excellent correlations despite only minor structural variations of the azulenes, which support this rather simple theoretical methodology for determining redox potentials of organic molecules. Furthermore, we have estimated the absolute redox potential of the ferrocene/ferrocenium redox couple to be 4.8 ± 0.1 V in dichloromethane, which is slightly lower than previous estimates.

U2 - 10.1039/c7cp08687c

DO - 10.1039/c7cp08687c

M3 - Journal article

C2 - 29484319

SN - 1463-9076

VL - 11

SP - 7438

EP - 7446

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

M1 - 20

ER -