Delocalization of Coherent Triplet Excitons in Linear Rigid Rod Conjugated Oligomers

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The Journal of Physical Chemistry Letters. 2017, 8(3), pp. 690-695. eISSN 1948-7185. Available under: doi: 10.1021/acs.jpclett.6b02869
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In this work, the triplet state delocalization in a series of monodisperse oligo(p-phenyleneethynylene)s (OPEs) is studied by pulsed electron paramagnetic resonance (EPR) and pulsed electron nuclear double resonance (ENDOR) determining zero-field splitting, optical spin polarization, and proton hyperfine couplings. Neither the zero-field splitting parameters nor the optical spin polarization change significantly with OPE chain length, in contrast to the hyperfine coupling constants, which showed a systematic decrease with chain length n according to a 2/(1 + n) decay law. The results provide striking evidence for the Frenkel-type nature of the triplet excitons exhibiting full coherent delocalization in the OPEs under investigation with up to five OPE repeat units and with a spin density distribution described by a nodeless particle in the box wave function. The same model is successfully applied to recently published data on π-conjugated porphyrin oligomers.

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ISO 690HINTZE, Christian, Patrick KORF, Frank DEGEN, Friederike SCHÜTZE, Stefan MECKING, Ulrich STEINER, Malte DRESCHER, 2017. Delocalization of Coherent Triplet Excitons in Linear Rigid Rod Conjugated Oligomers. In: The Journal of Physical Chemistry Letters. 2017, 8(3), pp. 690-695. eISSN 1948-7185. Available under: doi: 10.1021/acs.jpclett.6b02869
BibTex
@article{Hintze2017Deloc-38211,
  year={2017},
  doi={10.1021/acs.jpclett.6b02869},
  title={Delocalization of Coherent Triplet Excitons in Linear Rigid Rod Conjugated Oligomers},
  number={3},
  volume={8},
  journal={The Journal of Physical Chemistry Letters},
  pages={690--695},
  author={Hintze, Christian and Korf, Patrick and Degen, Frank and Schütze, Friederike and Mecking, Stefan and Steiner, Ulrich and Drescher, Malte}
}
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