A stable two-electron-donating phenothiazine for application in nonaqueous redox flow batteries

Jeffrey A. Kowalski; Matthew D. Casselman; Aman Preet Kaur; Jarrod D. Milshtein; Corrine F. Elliott; Subrahmanyam Modekrutti; N. Harsha Attanayake; Naijao Zhang; Sean R. Parkin; Chad Risko; Fikile R. Brushett; Susan A. Odom

doi:10.1039/c7ta05883g

A stable two-electron-donating phenothiazine for application in nonaqueous redox flow batteries

Jeffrey A. Kowalski, Matthew D. Casselman, Aman Preet Kaur, Jarrod D. Milshtein, Corrine F. Elliott, Subrahmanyam Modekrutti, N. Harsha Attanayake, Naijao Zhang, Sean R. Parkin, Chad Risko, Fikile R. Brushett, Susan A. Odom

Chemistry

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91 Scopus citations

Abstract

Stable electron-donating organic compounds are of interest for numerous applications that require reversible electron-transfer reactions. Although many organic compounds are stable one-electron donors, removing a second electron from a small molecule to form its dication usually leads to rapid decomposition. For cost-effective electrochemical energy storage utilizing organic charge-storage species, the creation of high-capacity materials requires stabilizing more charge whilst keeping molecular weights low. Here we report the simple modification of N-ethylphenothiazine, which is only stable as a radical cation (not as a dication), and demonstrate that introducing electron-donating methoxy groups para to nitrogen leads to dramatically improved stability of the doubly oxidized (dication) state. Our results reveal that this derivative is more stable than an analogous compound with substituents that do not allow for further charge delocalization, rendering it a promising scaffold for developing atom-efficient, two-electron donors.

Original language	English
Pages (from-to)	24371-24379
Number of pages	9
Journal	Journal of Materials Chemistry A
Volume	5
Issue number	46
DOIs	https://doi.org/10.1039/c7ta05883g
State	Published - 2017

Bibliographical note

Funding Information:
Molecular synthesis and characterization studies were supported by the National Science Foundation (NSF), Division of Chemistry under Award Number CHE-1300653 and through the Experimental Program to Stimulate Competitive Research (EPSCoR), Award Number 1355438. Electrochemical studies were supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. SAO and CR thank the University of Kentucky for start-up funds. JDM acknowledges additional financial support from the NSF Graduate Research Fellowship Program (DGE 1256260). CFE thanks the ACS Division of Organic Chemistry for a SURF award.

Funding Information:
Molecular synthesis and characterization studies were supported by the National Science Foundation (NSF), Division of Chemistry under Award Number CHE-1300653 and through the Experimental Program to Stimulate Competitive Research (EPSCoR), Award Number 1355438. Electrochemical studies were supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. SAO and CR thank the University of Kentucky for start-up funds. JDM acknowledges additional nancial support from the NSF Graduate Research Fellowship Program (DGE 1256260). CFE thanks the ACS Division of Organic Chemistry for a SURF award.

Publisher Copyright:
© 2017 The Royal Society of Chemistry.

ASJC Scopus subject areas

Chemistry (all)
Renewable Energy, Sustainability and the Environment
Materials Science (all)

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10.1039/c7ta05883g

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Kowalski, J. A., Casselman, M. D., Kaur, A. P., Milshtein, J. D., Elliott, C. F., Modekrutti, S., Attanayake, N. H., Zhang, N., Parkin, S. R., Risko, C., Brushett, F. R., & Odom, S. A. (2017). A stable two-electron-donating phenothiazine for application in nonaqueous redox flow batteries. Journal of Materials Chemistry A, 5(46), 24371-24379. https://doi.org/10.1039/c7ta05883g

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title = "A stable two-electron-donating phenothiazine for application in nonaqueous redox flow batteries",

abstract = "Stable electron-donating organic compounds are of interest for numerous applications that require reversible electron-transfer reactions. Although many organic compounds are stable one-electron donors, removing a second electron from a small molecule to form its dication usually leads to rapid decomposition. For cost-effective electrochemical energy storage utilizing organic charge-storage species, the creation of high-capacity materials requires stabilizing more charge whilst keeping molecular weights low. Here we report the simple modification of N-ethylphenothiazine, which is only stable as a radical cation (not as a dication), and demonstrate that introducing electron-donating methoxy groups para to nitrogen leads to dramatically improved stability of the doubly oxidized (dication) state. Our results reveal that this derivative is more stable than an analogous compound with substituents that do not allow for further charge delocalization, rendering it a promising scaffold for developing atom-efficient, two-electron donors.",

author = "Kowalski, {Jeffrey A.} and Casselman, {Matthew D.} and Kaur, {Aman Preet} and Milshtein, {Jarrod D.} and Elliott, {Corrine F.} and Subrahmanyam Modekrutti and Attanayake, {N. Harsha} and Naijao Zhang and Parkin, {Sean R.} and Chad Risko and Brushett, {Fikile R.} and Odom, {Susan A.}",

note = "Funding Information: Molecular synthesis and characterization studies were supported by the National Science Foundation (NSF), Division of Chemistry under Award Number CHE-1300653 and through the Experimental Program to Stimulate Competitive Research (EPSCoR), Award Number 1355438. Electrochemical studies were supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. SAO and CR thank the University of Kentucky for start-up funds. JDM acknowledges additional financial support from the NSF Graduate Research Fellowship Program (DGE 1256260). CFE thanks the ACS Division of Organic Chemistry for a SURF award. Funding Information: Molecular synthesis and characterization studies were supported by the National Science Foundation (NSF), Division of Chemistry under Award Number CHE-1300653 and through the Experimental Program to Stimulate Competitive Research (EPSCoR), Award Number 1355438. Electrochemical studies were supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. SAO and CR thank the University of Kentucky for start-up funds. JDM acknowledges additional nancial support from the NSF Graduate Research Fellowship Program (DGE 1256260). CFE thanks the ACS Division of Organic Chemistry for a SURF award. Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

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language = "English",

volume = "5",

pages = "24371--24379",

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AU - Kowalski, Jeffrey A.

AU - Casselman, Matthew D.

AU - Kaur, Aman Preet

AU - Milshtein, Jarrod D.

AU - Elliott, Corrine F.

AU - Modekrutti, Subrahmanyam

AU - Attanayake, N. Harsha

AU - Zhang, Naijao

AU - Parkin, Sean R.

AU - Risko, Chad

AU - Brushett, Fikile R.

AU - Odom, Susan A.

N1 - Funding Information: Molecular synthesis and characterization studies were supported by the National Science Foundation (NSF), Division of Chemistry under Award Number CHE-1300653 and through the Experimental Program to Stimulate Competitive Research (EPSCoR), Award Number 1355438. Electrochemical studies were supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. SAO and CR thank the University of Kentucky for start-up funds. JDM acknowledges additional financial support from the NSF Graduate Research Fellowship Program (DGE 1256260). CFE thanks the ACS Division of Organic Chemistry for a SURF award. Funding Information: Molecular synthesis and characterization studies were supported by the National Science Foundation (NSF), Division of Chemistry under Award Number CHE-1300653 and through the Experimental Program to Stimulate Competitive Research (EPSCoR), Award Number 1355438. Electrochemical studies were supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. SAO and CR thank the University of Kentucky for start-up funds. JDM acknowledges additional nancial support from the NSF Graduate Research Fellowship Program (DGE 1256260). CFE thanks the ACS Division of Organic Chemistry for a SURF award. Publisher Copyright: © 2017 The Royal Society of Chemistry.

PY - 2017

Y1 - 2017

N2 - Stable electron-donating organic compounds are of interest for numerous applications that require reversible electron-transfer reactions. Although many organic compounds are stable one-electron donors, removing a second electron from a small molecule to form its dication usually leads to rapid decomposition. For cost-effective electrochemical energy storage utilizing organic charge-storage species, the creation of high-capacity materials requires stabilizing more charge whilst keeping molecular weights low. Here we report the simple modification of N-ethylphenothiazine, which is only stable as a radical cation (not as a dication), and demonstrate that introducing electron-donating methoxy groups para to nitrogen leads to dramatically improved stability of the doubly oxidized (dication) state. Our results reveal that this derivative is more stable than an analogous compound with substituents that do not allow for further charge delocalization, rendering it a promising scaffold for developing atom-efficient, two-electron donors.

AB - Stable electron-donating organic compounds are of interest for numerous applications that require reversible electron-transfer reactions. Although many organic compounds are stable one-electron donors, removing a second electron from a small molecule to form its dication usually leads to rapid decomposition. For cost-effective electrochemical energy storage utilizing organic charge-storage species, the creation of high-capacity materials requires stabilizing more charge whilst keeping molecular weights low. Here we report the simple modification of N-ethylphenothiazine, which is only stable as a radical cation (not as a dication), and demonstrate that introducing electron-donating methoxy groups para to nitrogen leads to dramatically improved stability of the doubly oxidized (dication) state. Our results reveal that this derivative is more stable than an analogous compound with substituents that do not allow for further charge delocalization, rendering it a promising scaffold for developing atom-efficient, two-electron donors.

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IS - 46

ER -

A stable two-electron-donating phenothiazine for application in nonaqueous redox flow batteries

Abstract

Bibliographical note

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UN SDGs

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