The stabilizing role of intramolecular hydrogen bonding in disubstituted hydroxy-quinones

Armendáriz-Vidales, Georgina; Martínez‐González, Eduardo; Cuevas-Fernández, Héctor Javier; Fernández-Campos, Didier Omar; Burgos-Castillo, Rutely C.; Frontana, Carlos

doi:10.1016/j.electacta.2013.05.123

Cited by 21 publications

(27 citation statements)

References 21 publications

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“…This is due to a different treatment of electrostatic interactions (the main component of hydrogen bonding) in the two force fields [ 28 , 29 ]. The relationship between intramolecular hydrogen bonding and stability has been reported before [ 10 , 30 ].…”

Section: Computational Protocol and Resultsmentioning

confidence: 81%

A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials

Fornari

Silva

2021

Molecules

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Discovering new materials for energy storage requires reliable and efficient protocols for predicting key properties of unknown compounds. In the context of the search for new organic electrolytes for redox flow batteries, we present and validate a robust procedure to calculate the redox potentials of organic molecules at any pH value, using widely available quantum chemistry and cheminformatics methods. Using a consistent experimental data set for validation, we explore and compare a few different methods for calculating reaction free energies, the treatment of solvation, and the effect of pH on redox potentials. We find that the B3LYP hybrid functional with the COSMO solvation method, in conjunction with thermal contributions evaluated from BLYP gas-phase harmonic frequencies, yields a good prediction of pH = 0 redox potentials at a moderate computational cost. To predict how the potentials are affected by pH, we propose an improved version of the Alberty-Legendre transform that allows the construction of a more realistic Pourbaix diagram by taking into account how the protonation state changes with pH.

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Section: Computational Protocol and Resultsmentioning

confidence: 81%

A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials

Fornari

Silva

2021

Molecules

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“…The molecules with two redox units are named double redox (DR) and can exist in three forms: fully oxidized (A), partially reduced (AH 2 ) and fully reduced (AH 4 ). Those with three redox units (28)(29)(30)(31)(32)(33)(34)(35) are named triple redox (TR) have one further stable state (AH ). We assume that all redox processes are concerted twoelectron, two-proton reactions, as is the case for most quinonelike species.…”

Section: Toc Graphicsmentioning

confidence: 99%

“…For simplicity, we report the potential values determined by the more stable isomer of AH 2 , corresponding to the largest possible ΔU. We follow the same approach for the TR molecules (28)(29)(30)(31)(32)(33)(34)(35) and choose the most stable of the three isomers of the species AH 2 and AH 4 . In molecules 1-8, where the redox units are both quinones, ΔU is considerably larger than ΔU SR .…”

Section: Toc Graphicsmentioning

confidence: 99%

Molecular Engineering Strategies for Symmetric Aqueous Organic Redox Flow Batteries

Fornari

Mesta

Hjelm

et al. 2020

ACS Materials Lett.

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Symmetric aqueous organic redox flow batteries (RFBs) are potentially an inexpensive, durable, and safe energy storage technology. Unlike normal asymmetric flow batteries, they are based on electrolytes that exist in at least three oxidation states and can undergo a minimum of two distinct redox processes. We compute the redox potentials of selected electrolytes, with the intent to understand how the interaction between the redox units affects the potentials. We find that electronic interaction between redox units and intramolecular hydrogen bonding can be exploited to tune the difference between the redox potentials, i.e., the theoretical voltage of the battery. The redox potentials can be further fine-tuned in either direction by adding substituents. Starting from these observations, we formulate a set of rules that will help in finding ideal candidates for symmetric RFBs.

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“…27,28 The relationship between intramolecular hydrogen bonding and stability has been reported before. 10,29 Calculation of the redox potential at pH 0. For a general proton-coupled reduction reaction Ox +…”

Section: Initial Guess: Protonation and Conformermentioning

confidence: 99%

A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials

Fornari¹,

Silva

2021

Preprint

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<p>We present and validate a robust procedure to calculate the redox potentials of organic molecules at any pH value, using widely available quantum chemistry and cheminformatics methods. Using a consistent experimental data set for validation, we explore and compare a few different methods for calculating reaction free energies, the treatment of solvation, and the effect of pH on redox potentials. We find that the B3LYP hybrid functional with COSMO solvation method, in conjunction with thermal contributions evaluated from BLYP gas-phase harmonic frequencies, yields a good prediction of pH=0 redox potentials at a moderate computational cost. To predict how the potentials are affected by pH, we propose an improved version of the Alberty-Legendre transform that allows the construction of a more realistic Pourbaix diagram by taking into account how the protonation state changes with pH.</p>

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The stabilizing role of intramolecular hydrogen bonding in disubstituted hydroxy-quinones

Cited by 21 publications

References 21 publications

A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials

A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials

Molecular Engineering Strategies for Symmetric Aqueous Organic Redox Flow Batteries

A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials

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