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PreprintCC BYChemRxiv

Deterministic Preparation of Intermolecular Spin States Through Collective Light Emission in Copper Porphyrin Aggregates

  • Mandefro Y. Teferi1,2,3,4,5
  • Hasini Medagedara3,4,5
  • Jens Niklas1,2
  • Sachithra T. Wanasinghe3,4,5
  • Oleg G. Poluektov1,2
  • Aaron S. Rury3,4,5
5 affiliations
  1. 1Chemical Sciences and Engineering Division
  2. 2Argonne National Laboratory
  3. 3Materials Structural Dynamics Laboratory
  4. 4Wayne State University
  5. 5Department of Chemistry
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Abstract

The coupling of electron spins in open shell systems drives formation of distinct singlet and triplet states whose transitions possess unique coherence properties relative to those of doublets. Here we show that exchange interactions couple the electron spins on neighboring Cu cations within porphyrins macrocycles that participate in aggregate formation. Following photoexcitation, we find a ‘low field’ EPR signal whose peak position and shape are reproduced by simulations of anti-ferromagnetically coupled electron spins. We use time-resolved light emission and EPR results to propose that this ‘low field’ peak appears due to a singlet to triplet transition that results in selective, deterministic population of the lowest energy state in the coupled spin system. Our results highlight how enhanced radiative relaxation in molecular aggregates ligated with open shell transition metal cations can be used to design the coupled spin states that participate in EPR transitions. This design principle could be used to further extend the use of molecular chromophores in quantum information science and technology applications.

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Cite

BibTeXRIS
BibTeX
@misc{teferi2026deterministic,
  title = {{Deterministic Preparation of Intermolecular Spin States Through Collective Light Emission in Copper Porphyrin Aggregates}},
  author = {Mandefro Y. Teferi and Hasini Medagedara and Jens Niklas and Sachithra T. Wanasinghe and Oleg G. Poluektov and Aaron S. Rury},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010856/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010856/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Deterministic Preparation of Intermolecular Spin States Through Collective Light Emission in Copper Porphyrin Aggregates
AU  - Mandefro Y. Teferi
AU  - Hasini Medagedara
AU  - Jens Niklas
AU  - Sachithra T. Wanasinghe
AU  - Oleg G. Poluektov
AU  - Aaron S. Rury
PY  - 2026
DA  - 2026/10/22
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010856/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010856/v1
AB  - The coupling of electron spins in open shell systems drives formation of distinct singlet and triplet states whose transitions possess unique coherence properties relative to those of doublets. Here we show that exchange interactions couple the electron spins on neighboring Cu cations within porphyrins macrocycles that participate in aggregate formation. Following photoexcitation, we find a ‘low field’ EPR signal whose peak position and shape are reproduced by simulations of anti-ferromagnetically coupled electron spins. We use time-resolved light emission and EPR results to propose that this ‘low field’ peak appears due to a singlet to triplet transition that results in selective, deterministic population of the lowest energy state in the coupled spin system. Our results highlight how enhanced radiative relaxation in molecular aggregates ligated with open shell transition metal cations can be used to design the coupled spin states that participate in EPR transitions. This design principle could be used to further extend the use of molecular chromophores in quantum information science and technology applications.
ER  -