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Density function theory calculation to study the oxidation potential of electron-donating compounds; affirming the oxidation mechanism by NICS calculations

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Abstract

The manuscript describes a method for understanding the correlation of structural features and first oxidation potentials \(\left({E}_{ox}^{1}\right)\) of electron-donating compounds (EDCs) with tetrathiafulvalene (TTF), dithiadiazafulvalenes (DTDAF), and tetraazafulvalene (TAF) frameworks. The density functional theory (DFT) procedure at B3LYP (6–31 + g(d)) was used for geometric optimization, given the large dimensions of the molecules studied, and their high structural similarity. First of all, the correlation between the oxidation potential and the highest occupied molecular orbital (HOMO) energy level as an effective quantum chemical descriptor was examined. Then, nucleus-independent chemical shifts (NICSs) calculation was applied to affirm the oxidation mechanism and interpret the effect of replacing the sulfur atoms by nitrogen, on the oxidation process. Finally, a more comprehensive investigation of structural features that affect the oxidation potential, topological, geometrical, constitutional, as well as, electrostatic, charged partial surface area, quantum-chemical, molecular orbital, and thermodynamic descriptors was calculated. A predictive model was developed based on the genetic algorithm multivariate linear regression (GA-MLR). There was an outstanding agreement between the theoretical and the experimental values obtained for the first oxidation potentials of the test set (Q2Ext = 0.981).

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Authors and Affiliations

  1. Department of Chemistry, Payame Noor University (PNU), P.O. Box, 19395-3697, Tehran, Iran

    Abolghasem Beheshti

  2. Department of Chemistry, Faculty of Science, University of Mohaghegh Ardabili, P.O. Box 179, Ardabil, Iran

    Eslam Pourbasheer

  3. Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran

    Mohammad Reza Ganjali

  4. National Institute of Genetic Engineering and Biotechnology (NIGEB), Tehran, Iran

    Mohammad Reza Ganjali

Authors
  1. Abolghasem Beheshti
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  2. Eslam Pourbasheer
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  3. Mohammad Reza Ganjali
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Contributions

Abolghasem beheshti: supervising the overall research, DFT calculation, manuscript preparation. Eslam Pourbasheer: developed the QSPR, manuscript preparation. Mohammad Reza Ganjali: preparation of the manuscript. All authors reviewed the manuscript.

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Correspondence to Abolghasem Beheshti.

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Beheshti, A., Pourbasheer, E. & Ganjali, M.R. Density function theory calculation to study the oxidation potential of electron-donating compounds; affirming the oxidation mechanism by NICS calculations. J Mol Model 29, 32 (2023). https://doi.org/10.1007/s00894-022-05431-1

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