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Title: Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers

Journal Article · · Chemical Science
DOI: https://doi.org/10.1039/d0sc03567j · OSTI ID:1658637

Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially “quenching” conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.

Research Organization:
Texas A & M Univ., College Station, TX (United States); Cornell Univ., Ithaca, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0014006; SC0014336
OSTI ID:
1658637
Alternate ID(s):
OSTI ID: 1706079
Journal Information:
Chemical Science, Vol. 11, Issue 36; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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