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Issue 101, 2014
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Reduction potential predictions of some aromatic nitrogen-containing molecules

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Abstract

Accurate quantum chemical methods offer a reliable alternative to time-consuming experimental evaluations for obtaining a priori electrochemical knowledge of a large number of redox active molecules. In this contribution, quantum chemical calculations are performed to investigate the redox behavior of quinoxalines, a promising family of active materials for non-aqueous flow batteries, as a function of substituent group. The reduction potentials of 40 quinoxaline derivatives with a range of electron-donating and electron-withdrawing groups are computed. Calculations indicate the addition of electron-donating groups, particularly alkyl groups, can significantly lower the reduction potential albeit with a concomitant decrease in oxidative stability. A simple descriptor is derived for computing reduction potentials of quinoxaline derivatives from the LUMO energies of the neutral molecules without time-consuming free energy calculations. The relationship was validated for a broader set of aromatic nitrogen-containing molecules including pyrazine, phenazine, bipyridine, pyridine, pyrimidine, pyridazine, and quinoline, suggesting that it is a good starting point for large high-throughput computations to screen reduction windows of novel molecules.

Graphical abstract: Reduction potential predictions of some aromatic nitrogen-containing molecules

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The article was received on 12 Aug 2014, accepted on 17 Oct 2014 and first published on 20 Oct 2014


Article type: Paper
DOI: 10.1039/C4RA08563A
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RSC Adv., 2014,4, 57442-57451

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    Reduction potential predictions of some aromatic nitrogen-containing molecules

    R. S. Assary, F. R. Brushett and L. A. Curtiss, RSC Adv., 2014, 4, 57442
    DOI: 10.1039/C4RA08563A

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