Simple Air-Stable [3]Radialene Anion Radicals as Environmentally Switchable Catholytes in Water
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH..
The hexacyano[3]radialene radical anion (1) is an attractive catholyte material for use in redox flow battery (RFB) applications. The substitution of cyano groups with ester moieties enhances solubility while maintaining redox reversibility and favorable redox potentials. Here we show that these ester-functionalized, hexasubstituted [3]radialene radical anions dimerize reversibly in water. The dimerization mode is dependent on the substitution pattern and can be switched in solution. Stimuli-responsive behavior is achieved by exploiting an unprecedented tristate switching mechanism, wherein the radical can be toggled between the free radical, a π-dimer, and a σ-dimer-each with dramatically different optical, magnetic, and redox properties-by changing the solvent environment, temperature, or salinity. The symmetric, triester-tricyano[3]radialene (3) forms a solvent-responsive, σ-dimer in water that converts to the radical anion with the addition of organic solvents or to a π-dimer in brine solutions. Diester-tetracyano[3]radialene (2) exists primarily as a π-dimer in aqueous solutions and a radical anion in organic solvents. The dimerization behavior of both 2 and 3 is temperature dependent in methanol solutions. Dimerization equilibrium has a direct impact on catholyte stability during galvanostatic charge-discharge cycling in static H-cells. Specifically, conditions that favor the free radical anion or π-dimer exhibit significantly enhanced cycling profiles.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:30 |
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| Enthalten in: |
Chemistry (Weinheim an der Bergstrasse, Germany) - 30(2024), 7 vom: 01. Feb., Seite e202302829 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Hasan, Fuead [VerfasserIn] |
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| Links: |
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| Themen: |
Dimerization |
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| Anmerkungen: |
Date Revised 02.02.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/chem.202302829 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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NLM364604794 |
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| 520 | |a © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH. | ||
| 520 | |a The hexacyano[3]radialene radical anion (1) is an attractive catholyte material for use in redox flow battery (RFB) applications. The substitution of cyano groups with ester moieties enhances solubility while maintaining redox reversibility and favorable redox potentials. Here we show that these ester-functionalized, hexasubstituted [3]radialene radical anions dimerize reversibly in water. The dimerization mode is dependent on the substitution pattern and can be switched in solution. Stimuli-responsive behavior is achieved by exploiting an unprecedented tristate switching mechanism, wherein the radical can be toggled between the free radical, a π-dimer, and a σ-dimer-each with dramatically different optical, magnetic, and redox properties-by changing the solvent environment, temperature, or salinity. The symmetric, triester-tricyano[3]radialene (3) forms a solvent-responsive, σ-dimer in water that converts to the radical anion with the addition of organic solvents or to a π-dimer in brine solutions. Diester-tetracyano[3]radialene (2) exists primarily as a π-dimer in aqueous solutions and a radical anion in organic solvents. The dimerization behavior of both 2 and 3 is temperature dependent in methanol solutions. Dimerization equilibrium has a direct impact on catholyte stability during galvanostatic charge-discharge cycling in static H-cells. Specifically, conditions that favor the free radical anion or π-dimer exhibit significantly enhanced cycling profiles | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a dimerization | |
| 650 | 4 | |a radical ions | |
| 650 | 4 | |a redox chemistry | |
| 650 | 4 | |a sustainable chemistry | |
| 650 | 4 | |a water chemistry | |
| 700 | 1 | |a Gillen, Jonathan H |e verfasserin |4 aut | |
| 700 | 1 | |a Jayaweera, Amaya T |e verfasserin |4 aut | |
| 700 | 1 | |a McDearmon, William D |c Jr |e verfasserin |4 aut | |
| 700 | 1 | |a Winter, Arthur H |e verfasserin |4 aut | |
| 700 | 1 | |a Bejger, Christopher M |e verfasserin |4 aut | |
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