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

Literature Information

Publication Date 2018-02-19
DOI 10.1039/C7CP08687C
Impact Factor 3.676
Authors

Nicolai Ree, Cecilie Lindholm Andersen, Martin Drøhse Kilde, Ole Hammerich, Mogens Brøndsted Nielsen, Kurt V. Mikkelsen


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Abstract

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.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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