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Peer-reviewedCC BY 4.0Angewandte Chemie International Edition

Extending El Sayed's Rule by 1 (n,π*)– 3 (n,π*) Rotation via Intramolecular Secondary Interaction Enables Room‐Temperature Circularly Polarized Phosphorescence in Solution

  • Oscar Charpentier
  • Marie Guesdon
  • Catherine Demangeat
  • Maher Hojorat
  • Joseph Young
  • Emrys W Evans
  • Vincent Dorcet
  • Nicolas Galland
  • Denis Jacquemin
  • Ludovic Favereau
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Abstract

The development of purely organic chiral room temperature (RT) phosphorescent emitters is in the limelight. However, the key parameters governing the polarized luminescence are difficult to predict and rationalize since the phosphorescence emission is rarely obtained in solution, despite the introduction of heavy atoms (Br, I) or carbonyl groups, and engineering of total angular momentum, for example, singlet/triplet states corresponding to n-π*/π-π* transitions (or vice-versa), as prescribed by El-Sayed's rule. Here, we show that intramolecular secondary interactions can induce an efficient ISC between formally identical 1 (n,π*) and 3 (n,π*) states in chiral thionated phthalimide derivatives. This unprecedented type of inter-system crossing (ISC) extends the usual thinking of the El-Sayed principle and enables the realization of circularly polarized (CP) RT phosphorescence (RTP) in solution with g lum of up to 4 × 10 -3 . These results bring additional molecular design guidelines to reach CP-RTP in solution and offer new insights into the subtle relationships between excited states of different spin multiplicities that enable higher CP phosphorescence intensity.

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Cite

BibTeXRIS
BibTeX
@article{charpentier2026extending,
  title = {{Extending El Sayed's Rule by 1 (n,π*)– 3 (n,π*) Rotation via Intramolecular Secondary Interaction Enables Room‐Temperature Circularly Polarized Phosphorescence in Solution}},
  author = {Oscar Charpentier and Marie Guesdon and Catherine Demangeat and Maher Hojorat and Joseph Young and Emrys W Evans and Vincent Dorcet and Nicolas Galland and Denis Jacquemin and Ludovic Favereau},
  journal = {Angewandte Chemie International Edition},
  year = {2026},
  month = sep,
  doi = {10.1002/anie.8360226},
  url = {https://univ-rennes.hal.science/hal-05780683v1},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Extending El Sayed's Rule by 1 (n,π*)– 3 (n,π*) Rotation via Intramolecular Secondary Interaction Enables Room‐Temperature Circularly Polarized Phosphorescence in Solution
AU  - Oscar Charpentier
AU  - Marie Guesdon
AU  - Catherine Demangeat
AU  - Maher Hojorat
AU  - Joseph Young
AU  - Emrys W Evans
AU  - Vincent Dorcet
AU  - Nicolas Galland
AU  - Denis Jacquemin
AU  - Ludovic Favereau
PY  - 2026
DA  - 2026/09/23
JO  - Angewandte Chemie International Edition
DO  - 10.1002/anie.8360226
UR  - https://univ-rennes.hal.science/hal-05780683v1
AB  - The development of purely organic chiral room temperature (RT) phosphorescent emitters is in the limelight. However, the key parameters governing the polarized luminescence are difficult to predict and rationalize since the phosphorescence emission is rarely obtained in solution, despite the introduction of heavy atoms (Br, I) or carbonyl groups, and engineering of total angular momentum, for example, singlet/triplet states corresponding to n-π*/π-π* transitions (or vice-versa), as prescribed by El-Sayed's rule. Here, we show that intramolecular secondary interactions can induce an efficient ISC between formally identical 1 (n,π*) and 3 (n,π*) states in chiral thionated phthalimide derivatives. This unprecedented type of inter-system crossing (ISC) extends the usual thinking of the El-Sayed principle and enables the realization of circularly polarized (CP) RT phosphorescence (RTP) in solution with g lum of up to 4 × 10 -3 . These results bring additional molecular design guidelines to reach CP-RTP in solution and offer new insights into the subtle relationships between excited states of different spin multiplicities that enable higher CP phosphorescence intensity.
SN  - 1433-7851
SN  - 1521-3773
ER  -