Theoretical Investigation of the Substituent Effect on First and Second Reduction Potential of Benzoquinone Derivatives: From a DFT Perspective for Redox Flow Battery Application.
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| Title: | Theoretical Investigation of the Substituent Effect on First and Second Reduction Potential of Benzoquinone Derivatives: From a DFT Perspective for Redox Flow Battery Application. |
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| Authors: | Yimam, Getahun Bayou1 (AUTHOR), Gemechu, Desalegn Nigatu1 (AUTHOR) desalegn.nigatu@aau.edu.et, Chaka, Mesfin Diro2 (AUTHOR), Desta, Mekonnen Abebayehu1 (AUTHOR), Mohammed, Ahmed Mustefa1 (AUTHOR), Mekonnen, Yedilfana Satarge1 (AUTHOR) yedilfana.setarge@aau.edu.et |
| Source: | Journal of Physical Organic Chemistry. Jul2026, Vol. 39 Issue 7, p1-11. 11p. |
| Subjects: | Reduction potential, Lewis acidity, Benzoquinones, Polar effects (Chemistry), Vanadium redox battery, Density functional theory, Electron donors |
| Abstract: | This study investigated the electrochemical behavior of benzoquinone (BQ) and its derivatives using density functional theory (DFT) calculations at the B3LYP/6‐311+G(d) level of theory. The first and second reduction potentials of BQ and its derivatives were predicted in both gas and solvent phases, water, dimethyl sulfoxide (DMSO), and cyclohexane. The solvation free energies were determined using the conductor‐like polarizable continuum model (CPCM), highlighting the significant influence of solvent effects on the redox potentials. The DFT results reveal that electron‐withdrawing group (EWG)‐substituted BQs exhibit higher first and second reduction potentials compared to electron‐donating group (EDG)‐substituted derivatives. Specifically, –NO2 shows first and second reduction potentials of 3.24 and 2.58 V, respectively, while –CN exhibits 3.22 and 2.51 V, and –CF3 shows 3.19 and 2.43 V, respectively, in water. In contrast, EDG‐substituted BQs such as –NH2 (2.86 and 2.12 V) and –OH (2.91 and 2.05 V) display comparatively lower reduction potentials. These trends reflect the influence of substituents on the electronic structure of the redox‐active quinone core, where EWGs reduce electron density and stabilize the reduced species, thereby increasing the reduction potential, whereas EDGs increase electron density and lower the reduction potential. Furthermore, coordination with Lewis acids and their decomposition products significantly enhances the reduction potentials of BQ. The calculated first and second reduction potentials are 6.07 and 3.95 V for BF3, 5.82 and 3.71 V for BCl3, and 6.35 and 4.28 V for AlF3, respectively. These results indicate that metal–Lewis acid interactions can substantially modulate the electrochemical properties of quinone systems. Unlike previous studies focusing primarily on single‐electron reduction processes, this work provides a unified DFT framework that simultaneously evaluates substituent effects, solvent polarity, and Lewis acid coordination on both first and second reduction processes of BQ derivatives. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 194673014 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Theoretical Investigation of the Substituent Effect on First and Second Reduction Potential of Benzoquinone Derivatives: From a DFT Perspective for Redox Flow Battery Application. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Yimam%2C+Getahun+Bayou%22">Yimam, Getahun Bayou</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Gemechu%2C+Desalegn+Nigatu%22">Gemechu, Desalegn Nigatu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> desalegn.nigatu@aau.edu.et</i><br /><searchLink fieldCode="AR" term="%22Chaka%2C+Mesfin+Diro%22">Chaka, Mesfin Diro</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Desta%2C+Mekonnen+Abebayehu%22">Desta, Mekonnen Abebayehu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Mohammed%2C+Ahmed+Mustefa%22">Mohammed, Ahmed Mustefa</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Mekonnen%2C+Yedilfana+Satarge%22">Mekonnen, Yedilfana Satarge</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> yedilfana.setarge@aau.edu.et</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Organic+Chemistry%22">Journal of Physical Organic Chemistry</searchLink>. Jul2026, Vol. 39 Issue 7, p1-11. 11p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Reduction+potential%22">Reduction potential</searchLink><br /><searchLink fieldCode="DE" term="%22Lewis+acidity%22">Lewis acidity</searchLink><br /><searchLink fieldCode="DE" term="%22Benzoquinones%22">Benzoquinones</searchLink><br /><searchLink fieldCode="DE" term="%22Polar+effects+%28Chemistry%29%22">Polar effects (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Vanadium+redox+battery%22">Vanadium redox battery</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+donors%22">Electron donors</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: This study investigated the electrochemical behavior of benzoquinone (BQ) and its derivatives using density functional theory (DFT) calculations at the B3LYP/6‐311+G(d) level of theory. The first and second reduction potentials of BQ and its derivatives were predicted in both gas and solvent phases, water, dimethyl sulfoxide (DMSO), and cyclohexane. The solvation free energies were determined using the conductor‐like polarizable continuum model (CPCM), highlighting the significant influence of solvent effects on the redox potentials. The DFT results reveal that electron‐withdrawing group (EWG)‐substituted BQs exhibit higher first and second reduction potentials compared to electron‐donating group (EDG)‐substituted derivatives. Specifically, –NO2 shows first and second reduction potentials of 3.24 and 2.58 V, respectively, while –CN exhibits 3.22 and 2.51 V, and –CF3 shows 3.19 and 2.43 V, respectively, in water. In contrast, EDG‐substituted BQs such as –NH2 (2.86 and 2.12 V) and –OH (2.91 and 2.05 V) display comparatively lower reduction potentials. These trends reflect the influence of substituents on the electronic structure of the redox‐active quinone core, where EWGs reduce electron density and stabilize the reduced species, thereby increasing the reduction potential, whereas EDGs increase electron density and lower the reduction potential. Furthermore, coordination with Lewis acids and their decomposition products significantly enhances the reduction potentials of BQ. The calculated first and second reduction potentials are 6.07 and 3.95 V for BF3, 5.82 and 3.71 V for BCl3, and 6.35 and 4.28 V for AlF3, respectively. These results indicate that metal–Lewis acid interactions can substantially modulate the electrochemical properties of quinone systems. Unlike previous studies focusing primarily on single‐electron reduction processes, this work provides a unified DFT framework that simultaneously evaluates substituent effects, solvent polarity, and Lewis acid coordination on both first and second reduction processes of BQ derivatives. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1002/poc.70085 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 11 StartPage: 1 Subjects: – SubjectFull: Reduction potential Type: general – SubjectFull: Lewis acidity Type: general – SubjectFull: Benzoquinones Type: general – SubjectFull: Polar effects (Chemistry) Type: general – SubjectFull: Vanadium redox battery Type: general – SubjectFull: Density functional theory Type: general – SubjectFull: Electron donors Type: general Titles: – TitleFull: Theoretical Investigation of the Substituent Effect on First and Second Reduction Potential of Benzoquinone Derivatives: From a DFT Perspective for Redox Flow Battery Application. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Yimam, Getahun Bayou – PersonEntity: Name: NameFull: Gemechu, Desalegn Nigatu – PersonEntity: Name: NameFull: Chaka, Mesfin Diro – PersonEntity: Name: NameFull: Desta, Mekonnen Abebayehu – PersonEntity: Name: NameFull: Mohammed, Ahmed Mustefa – PersonEntity: Name: NameFull: Mekonnen, Yedilfana Satarge IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 07 Text: Jul2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 08943230 Numbering: – Type: volume Value: 39 – Type: issue Value: 7 Titles: – TitleFull: Journal of Physical Organic Chemistry Type: main |
| ResultId | 1 |
