Issue 14, 2022

Mesolytic cleavage of homobenzylic ethers for programmable end-of-life function in redoxmers

Abstract

Irreparable chemical damage to redox-active monomers, oligomers, and polymers (i.e. redoxmers) limits the lifetime of energy storage devices (e.g. redox flow batteries) by causing electrode and membrane fouling, as well as irreversible capacity loss. To predictably restore device and materials performance, it is desirable to add programmed destruction capabilities into these damage-prone materials. Here, we report the use of triggerable retrograde reactions to achieve programmable end-of-life function in redoxmers. Retrograde reactions are intended to break up damaged redoxmer materials into more soluble small-molecule constituents to prevent irreparably fouling battery interfaces. We investigated the redox-triggered mesolytic cleavage of homobenzylic ethers (HBEs) for this purpose. Combining experimental methods with simulations, we probed the influence of ring substituents on the programmable bond-scission behavior of HBEs. Variation of para-substituents on the HBEs allowed us to modify the oxidation potential, degradation pathway, and electrochemical mechanisms of the generated products. Given its ideal oxidation potential, we selected the para-methoxy-based HBE as the cleavage scaffold and integrated it with dialkoxybenzene, TEMPO, viologen, and para-nitrobenzene redox centers for compatibility, bulk deconstruction, and electrode defouling tests. Upon applying a high oxidation potential, the redox-active pendant is cleaved from the backbone via HBE bonds; of the four redox centers tested, three of them remained fully redox active. Viologen-appended redox active polymers with HBE linkers were cleaved to fully separate the redox centers from the backbone. Polymer-filmed electrodes were partially restored following HBE oxidation defouling. These studies highlight the co-design of new materials functions for developing sustainable energy storage materials.

Graphical abstract: Mesolytic cleavage of homobenzylic ethers for programmable end-of-life function in redoxmers

Supplementary files

Article information

Article type
Paper
Submitted
01 дек 2021
Accepted
26 фев 2022
First published
07 мар 2022

J. Mater. Chem. A, 2022,10, 7739-7753

Author version available

Mesolytic cleavage of homobenzylic ethers for programmable end-of-life function in redoxmers

H. Qian, M. J. Counihan, H. A. Doan, N. A. Ibrahim, A. S. Danis, W. Setwipatanachai, N. S. Purwanto, J. Rodríguez-López, R. S. Assary and J. S. Moore, J. Mater. Chem. A, 2022, 10, 7739 DOI: 10.1039/D1TA10291E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements