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Peer-reviewedCC BY 4.0Angewandte Chemie (International Ed. in English)

Hydrogen‐Bonding Order Associated With Radical Delocalization in Layered Organic Cathode Materials

  • Alae Eddine Lakraychi1,2,3
  • Zeqian Zhang1,4,5
  • Oliver Lin6,7
  • Eric D Walter1,5
  • Jiaqi Wang1,8
  • Harshan Reddy Gopidi1,2,3
  • Eliot F. Woods1,9
  • Ruozhu Feng1,9
  • Wei Wang1,9
  • Pieremanuele Canepa1,2,3
  • Brett A. Helms1,10,11
  • Kamila M. Wiaderek1,8
3 more authors
  • Qian Chen6,7,12
  • Yan Yao1,2,3,13,14
  • Ying Chen1,5
14 affiliations
  1. 1Energy Storage Research Alliance Argonne National Laboratory Lemont Illinois USA
  2. 2Department of Electrical and Computer Engineering University of Houston Houston Texas USA
  3. 3Texas Center for Superconductivity University of Houston Houston Texas USA
  4. 4Department of Chemistry University of Washington Seattle Washington USA
  5. 5Physical and Computational Sciences Directorate Pacific Northwest National Laboratory Richland Washington USA
  6. 6Department of Chemistry University of Illinois Urbana Illinois USA
  7. 7Materials Research Laboratory University of Illinois Urbana Illinois USA
  8. 8X‐ray Science Division Argonne National Laboratory Lemont Illinois USA
  9. 9Energy and Environment Directorate Pacific Northwest National Laboratory Richland Washington USA
  10. 10The Molecular Foundry Lawrence Berkeley National Laboratory Berkeley California USA
  11. 11Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley California USA
  12. 12Department of Materials Science and Engineering University of Illinois Urbana Illinois USA
  13. 13Department of Earth and Environmental Engineering Columbia University New York New York USA
  14. 14Columbia Climate School Columbia University New York New York USA
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Abstract

Organic electrode materials (OEMs) offer a sustainable alternative to inorganic cathodes but typically suffer from low intrinsic electronic conductivity. The material historically reported as bis‐tetraaminobenzoquinone (TAQ) exhibits bulk conductivity two orders of magnitude higher than its close analogue tetraaminophenazine‐tetraone (TAPT), despite their common precursor and nearly identical short‐range structure. This disparity has previously been attributed to distinct molecular skeletons, with TAQ proposed to adopt a piperazine‐type linkage and TAPT a pyrazine ring. Here, combining synchrotron x‐ray scattering, solid‐state 15N and 13C nuclear magnetic resonance (NMR), microcrystal electron diffraction (MicroED), continuous‐wave and pulsed electron paramagnetic resonance (EPR) spectroscopy, we show that “TAQ” has the same pyrazine‐based molecular structure as TAPT, with no evidence for piperazine core or keto–enol tautomerization. Their key difference lies in synthesis‐dependent degree of crystallinity: “TAQ” exhibits greater long‐range structural coherence and a crystallographically resolved intermolecular hydrogen‐bonding network, whereas TAPT is more disordered. EPR further shows that the higher structural order in “TAQ” is associated with a strongly delocalized π‐spin manifold, while TAPT favors localized or weakly delocalized radicals and stronger local spin coupling. These findings identify degree of crystallinity and hydrogen‐bonding order as key structural features associated with radical delocalization and enhanced conductivity in organic electrodes.

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Cite

BibTeXRIS
BibTeX
@article{lakraychi2026hydrogenbonding,
  title = {{Hydrogen‐Bonding Order Associated With Radical Delocalization in Layered Organic Cathode Materials}},
  author = {Alae Eddine Lakraychi and Zeqian Zhang and Oliver Lin and Eric D Walter and Jiaqi Wang and Harshan Reddy Gopidi and Eliot F. Woods and Ruozhu Feng and Wei Wang and Pieremanuele Canepa and Brett A. Helms and Kamila M. Wiaderek and Qian Chen and Yan Yao and Ying Chen},
  journal = {Angewandte Chemie (International Ed. in English)},
  year = {2026},
  month = sep,
  doi = {10.1002/anie.2483808},
  url = {https://doi.org/10.1002/anie.2483808},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Hydrogen‐Bonding Order Associated With Radical Delocalization in Layered Organic Cathode Materials
AU  - Alae Eddine Lakraychi
AU  - Zeqian Zhang
AU  - Oliver Lin
AU  - Eric D Walter
AU  - Jiaqi Wang
AU  - Harshan Reddy Gopidi
AU  - Eliot F. Woods
AU  - Ruozhu Feng
AU  - Wei Wang
AU  - Pieremanuele Canepa
AU  - Brett A. Helms
AU  - Kamila M. Wiaderek
AU  - Qian Chen
AU  - Yan Yao
AU  - Ying Chen
PY  - 2026
DA  - 2026/09/16
JO  - Angewandte Chemie (International Ed. in English)
DO  - 10.1002/anie.2483808
UR  - https://doi.org/10.1002/anie.2483808
AB  - Organic electrode materials (OEMs) offer a sustainable alternative to inorganic cathodes but typically suffer from low intrinsic electronic conductivity. The material historically reported as bis‐tetraaminobenzoquinone (TAQ) exhibits bulk conductivity two orders of magnitude higher than its close analogue tetraaminophenazine‐tetraone (TAPT), despite their common precursor and nearly identical short‐range structure. This disparity has previously been attributed to distinct molecular skeletons, with TAQ proposed to adopt a piperazine‐type linkage and TAPT a pyrazine ring. Here, combining synchrotron x‐ray scattering, solid‐state 15N and 13C nuclear magnetic resonance (NMR), microcrystal electron diffraction (MicroED), continuous‐wave and pulsed electron paramagnetic resonance (EPR) spectroscopy, we show that “TAQ” has the same pyrazine‐based molecular structure as TAPT, with no evidence for piperazine core or keto–enol tautomerization. Their key difference lies in synthesis‐dependent degree of crystallinity: “TAQ” exhibits greater long‐range structural coherence and a crystallographically resolved intermolecular hydrogen‐bonding network, whereas TAPT is more disordered. EPR further shows that the higher structural order in “TAQ” is associated with a strongly delocalized π‐spin manifold, while TAPT favors localized or weakly delocalized radicals and stronger local spin coupling. These findings identify degree of crystallinity and hydrogen‐bonding order as key structural features associated with radical delocalization and enhanced conductivity in organic electrodes.
SN  - 1433-7851
SN  - 1521-3773
ER  -