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Theoretical study on redox potentials of organic radicals in different solvents

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Abstract

The BMK density functional theory method has been used to examine the redox potentials of organic radicals in different solvents (DMF, N,N-dimethylformamide; DMSO, dimethyl sulfoxide; MeCN, acetonitrile). The polarizable continuum solvation model (PCM) was used to describe the solvation-free energies. The one-electron electrochemical standard potentials (E 0) of ca. 100 organic radicals in three solvents were calculated using a single, unified theoretical method whose reliability has been tested against almost all the available experimental data. It was found that the mean absolute deviation (MAD) between the theory and experiment was about 0.08 V. With the newly developed theoretical method in hand, more redox potentials of organic radicals in these three solvents were predicted by this single, unified method. The results showed that the redox potentials of organic radicals in different organic solvents including DMF and DMSO had good correlations with their redox potentials in MeCN.

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Acknowledgements

This study was supported by the National Natural Science Foundation of China (No.20602034), Anhui Provincial Natural Science Foundation (No.070416237) and the Excellent Young Scholars Foundation of Anhui Province (No. 08040106829). We also thank the USTC-HP, Shanghai Supercomputer Center, for the computational resources.

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  1. Tianjin EconomicTechnological Development Area Polytechinc, Tianjin, 300457, China

    Huajing Wang & Chaojing Yu

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  1. Huajing Wang
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Correspondence to Huajing Wang.

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Wang, H., Yu, C. Theoretical study on redox potentials of organic radicals in different solvents. Res Chem Intermed 36, 1003–1019 (2010). https://doi.org/10.1007/s11164-010-0212-8

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