Dataset Information

Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials.

ABSTRACT: Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the practical cyclic voltammetry (CV) measurements, it is shown that the redox potentials (E_1/2) of the 1,2,4,5-tetrazines (s-tetrazines) have a strong correlation with the Hammett constant of the substituents. In Li-ion coin cells, the discharge voltages of the s-tetrazine electrodes are successfully tuned depending on the electron-donating/withdrawing capabilities of the substituents. Furthermore, it is found that the heterogeneous electron transfer rate (k₀) of the s-tetrazine molecules and Li-ion diffusivity (D_Li) in the s-tetrazine electrodes are much faster than conventional electrode active materials.

SUBMITTER: Min DJ

PROVIDER: S-EPMC7914744 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials.

Min Dong Joo DJ Lee Kyunam K Park Hyunji H Kwon Ji Eon JE Park Soo Young SY

Molecules (Basel, Switzerland) 20210208 4

Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the practical cyclic voltammetry (CV) measurements, it is shown that the redox potentials (E<sub>1/2</sub>) of the 1,2,4,5-tetrazines (s-tetrazines) have a strong correlation with the Ham ...[more]

PMID: 33567761

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Project description:The central role of Coulombic interactions in enzyme catalysis has inspired multiple approaches to sculpting electrostatic potential fields (EPFs) for controlling chemical reactivity, including ion gradients in water microdroplets, the tips of STMs, and precisely engineered crystals. These are powerful tools because EPFs can affect all reactions, even those whose mechanisms do not involve formal charges. For some time now, supramolecular chemists have become increasingly proficient in using encapsulation to control stoichiometric and catalytic reactions. However, the field has not taken advantage of the broad range of nanocontainers available to systematically explore how EPFs can affect reactions within their inner-spaces. With that idea in mind, previously, we reported on how positively and negatively charged supramolecular capsules can modulate the acidity and reactivity of thiol guests bound within their inner, yoctoliter spaces (Cai, X.; Kataria, R.; Gibb, B. C. J. Am. Chem. Soc. 2020, 142, 8291-8298; Wang, K.; Cai, X.; Yao, W.; Tang, D.; Kataria, R.; Ashbaugh, H. S.; Byers, L. D.; Gibb, B. C. J. Am. Chem. Soc. 2019, 141, 6740-6747). Building on this, we report here on the cyclization of 14-bromotetradecan-1-amine inside these yoctoliter containers. We examine the rate and activation thermodynamics of cyclization (Eyring analysis), both in the absence and presence of exogenous salts whose complementary ion can bind to the outside of the capsule and hence attenuate its EPF. We find the cyclization rates and activation thermodynamics in the two capsules to be similar, but that for either capsule attenuation of the EPF slows the reaction down considerably. We conclude the capsules behave in a manner akin to covalently attached electron donating/withdrawing groups in a substrate, with each capsule enforcing their own deviations from the idealized SN2 mechanism by moving electron density and charge in the activated complex and TS, and that the idealized SN2 mechanism inside the theoretical neutral host is relatively difficult because of the lack of solvation of the TS.

Dataset Information

Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials.

Publications

Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials.

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