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Theoretical prediction for redox potentials of oxygen-centered organic anions in aprotic solvents

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Abstract

It is well known that the feasibility of electron transfer reactions and the thermodynamic relationship between radicals and anions are highly dependent on the standard redox potentials. However, due to experimental limitations on the measurement of irreversible redox reactions, it is often difficult or even impossible to obtain reliable oxidation or reduction potential data. In this study, we assessed the performance of different theoretical methods and solvation models for predicting standard oxidation potentials (\({E}_{\mathrm{ox}}^{\mathrm{o}}\)) of 33 representative anions including alcoholate, phenolate, and carboxylate anions in aprotic polar solvents. The density functional theory (DFT) M06-2X method and the composite procedure CBS-QB3 both achieved ideal precision for predicting adiabatic ionization potentials (IPs) in the gas phase, with a mean absolute deviation (MAD) value of 0.06 eV and 0.08 eV, respectively. As for solvation contributions, the SMD (solvation model density) model performed better than the latest uESE (Universal Easy Solvation Energy Evaluation) model for this kind of radical/anion couple. We suggest the optimal combination of M06-2X/ma-TZVP for IPs, and the SMD solvation model at M05-2X/6-31G(d) level is suitable for predicting \({E}_{\mathrm{ox}}^{\mathrm{o}}\), with an average error of 0.08 V. This assessment provides an alternative and reliable theoretical procedure to predict the oxidation potential and other related thermodynamic properties of O-centered organic anions.

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All data generated or analyzed during this study are included in this published article and its supplementary information files.

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Acknowledgements

Financial support from National Natural Science Foundation of China (NSFC 21927814) and generous support by the School of Pharmaceutical Science and Technology, Tianjin University, China, including computer time on the SPST computer cluster Arran are gratefully acknowledged.

Funding

This work was supported by National Natural Science Foundation of China (NSFC 21927814).

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  1. School of Pharmaceutical Science and Technology, Tianjin University, Tianjin, 300072, China

    Xinhong Wang, Fangya Li & Jianyu Zhang

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  1. Xinhong Wang
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  2. Fangya Li
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All authors contributed to the study conception and design. JZ designed the experiments. XW performed the experiments. XW and JZ analyzed the data and wrote the manuscript. All authors reviewed the manuscript.

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Correspondence to Jianyu Zhang.

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Wang, X., Li, F. & Zhang, J. Theoretical prediction for redox potentials of oxygen-centered organic anions in aprotic solvents. Theor Chem Acc 142, 62 (2023). https://doi.org/10.1007/s00214-023-03002-y

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