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Peer-reviewedCC BYJournal of the American Chemical Society

Highly Charged Porphyrin Molecular Wires.

  • Janko Hergenhahn1,2
  • Sebastian M Kopp1,2
  • Edward R Champness1,2
  • Damyan Frantzov2
  • Kavita Rani2
  • Arzhang Ardavan3
  • Harry L Anderson2
  • Christiane R Timmel1,2
  1. 1Centre for Advanced Electron Spin Resonance, Department of Chemistry, University of Oxford, OxfordOX1 3QR, U.K.
  2. 2Chemistry Research Laboratory, Department of Chemistry, University of Oxford, OxfordOX1 3TA, U.K.
  3. 3The Clarendon Laboratory, Department of Physics, University of Oxford, Parks Road, OxfordOX1 3PU, U.K.
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Abstract

Successive oxidations, or reductions, of an extended molecular π-system can give rise to significant changes in the electronic structure compared to the neutral or singly charged counterparts. In this work, we investigated highly reduced states of butadiyne-linked porphyrin oligomers with up to nine porphyrin units and one negative charge per porphyrin. CW-EPR and 1H Mims ENDOR spectroscopy were used to probe the proton hyperfine interactions in these polyanions. Both techniques show a continuous narrowing of the spectra with simultaneously increasing charge and oligomer length corresponding to a decrease in the magnitudes of the largest hyperfine interactions. This is consistent with density functional theory calculations that support delocalization of spin density over the entire lengths of the molecules with high degrees of spin polarization and nonuniform spin density distributions. These spin distributions can also be described by a Hubbard model with antiferromagnetic spin coupling between electrons on adjacent sites. Finding systems with coherent wave functions that span the entire length of π-conjugated molecules, up to a length of more than 10 nm, will help identifying suitable candidates capable of coherent electron tunneling through molecular junctions.

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Cite

BibTeXRIS
BibTeX
@article{hergenhahn2026highly,
  title = {{Highly Charged Porphyrin Molecular Wires.}},
  author = {Janko Hergenhahn and Sebastian M Kopp and Edward R Champness and Damyan Frantzov and Kavita Rani and Arzhang Ardavan and Harry L Anderson and Christiane R Timmel},
  journal = {Journal of the American Chemical Society},
  year = {2026},
  month = sep,
  doi = {10.1021/jacs.6c09441},
  url = {https://europepmc.org/article/MED/42915512},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Highly Charged Porphyrin Molecular Wires.
AU  - Janko Hergenhahn
AU  - Sebastian M Kopp
AU  - Edward R Champness
AU  - Damyan Frantzov
AU  - Kavita Rani
AU  - Arzhang Ardavan
AU  - Harry L Anderson
AU  - Christiane R Timmel
PY  - 2026
DA  - 2026/09/01
JO  - Journal of the American Chemical Society
DO  - 10.1021/jacs.6c09441
UR  - https://europepmc.org/article/MED/42915512
AB  - Successive oxidations, or reductions, of an extended molecular π-system can give rise to significant changes in the electronic structure compared to the neutral or singly charged counterparts. In this work, we investigated highly reduced states of butadiyne-linked porphyrin oligomers with up to nine porphyrin units and one negative charge per porphyrin. CW-EPR and 1H Mims ENDOR spectroscopy were used to probe the proton hyperfine interactions in these polyanions. Both techniques show a continuous narrowing of the spectra with simultaneously increasing charge and oligomer length corresponding to a decrease in the magnitudes of the largest hyperfine interactions. This is consistent with density functional theory calculations that support delocalization of spin density over the entire lengths of the molecules with high degrees of spin polarization and nonuniform spin density distributions. These spin distributions can also be described by a Hubbard model with antiferromagnetic spin coupling between electrons on adjacent sites. Finding systems with coherent wave functions that span the entire length of π-conjugated molecules, up to a length of more than 10 nm, will help identifying suitable candidates capable of coherent electron tunneling through molecular junctions.
SN  - 0002-7863
SN  - 1520-5126
ER  -