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Radical anions of quinoxalines (an in situ electron paramagnetic resonance spectroelectrochemical and theoretical study)

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Abstract

The cathodic reduction of 10-ethyl-7H,10H-pyrido[2,3-f]quinoxalin-7-one (1a) and ethyl 10-ethyl-7-oxo-7H,10H-pyrido[2,3-f]quinoxaline-8-carboxylate (2a), as well as their 2,3-R,R-substituted derivatives (R = CH3 or C6H5), represents a reversible one-electron process coupled with the generation of corresponding radical monoanions as evidenced by in situ electron paramagnetic resonance (EPR)/UV–vis-near-infrared (NIR) cyclovoltammetric experiments in N,N-dimethylformamide. The detected radical monoanions are characterized by electronic absorption bands in the vis-NIR regions, and their EPR spectra show a dominant interaction of the unpaired electron with the nitrogen and hydrogen nuclei of the pyrazine ring. The reduction behavior of 10-ethyl-7-oxo-7H,10H-pyrido[2,3-f]quinoxaline-8-carboxylic acid (3a) and its 2,3-dimethyl or 2,3-diphenyl derivatives is more complex, revealing an irreversible first reduction peak, followed by a second reversible reduction step. Based on the results of the in situ EPR/UV–vis-NIR spectroelectrochemical measurements for quinoxaline carboxylic acids, the first irreversible reduction peak was assigned to a reduction process on the pyridone ring, followed by a second reversible reduction process on the π-electron deficient pyrazine moiety, generating the radical monoanions detected by EPR spectroscopy.

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Acknowledgments

This work was supported by the Research and Development Agency of the Slovak Republic (contract nos. APVV-0339-10, APVV-0038-11) and the Scientific Grant Agency of the Slovak Republic (Projects VEGA/1/0289/12, VEGA/1/0829/14, VEGA/1/0735/13 and VEGA/1/0307/14). Philip Grier is gratefully acknowledged for helpful discussion.

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Authors and Affiliations

  1. Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovakia

    Karol Lušpai, Andrej Staško, Vladimír Lukeš, Dana Dvoranová, Zuzana Barbieriková, Peter Rapta & Vlasta Brezová

  2. Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-845 38, Bratislava, Slovakia

    Maroš Bella

  3. Institute of Organic Chemistry, Catalysis and Petrochemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovakia

    Viktor Milata

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  1. Karol Lušpai
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  2. Andrej Staško
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Correspondence to Vlasta Brezová.

Additional information

Dedicated to the memory of Professor Lothar Dunsch.

The paper represents the applications of unique techniques developed during a long-time cooperation between our Institute of Physical Chemistry in Bratislava and Department of Electrochemistry and Conducting Polymers of IFW in Dresden headed by Professor Dunsch, coupled with an exchange program which has facilitated numerous students and scientists to improve their skills and develop expertise in the field of spectroelectrochemistry.

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Lušpai, K., Staško, A., Lukeš, V. et al. Radical anions of quinoxalines (an in situ electron paramagnetic resonance spectroelectrochemical and theoretical study). J Solid State Electrochem 19, 113–122 (2015). https://doi.org/10.1007/s10008-014-2625-6

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  • DOI: https://doi.org/10.1007/s10008-014-2625-6

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