Positive electronic exchange interaction and predominance of minor triplet channel in CIDNP formation in short lived charge separated states of D-X-A dyads

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2020
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Zhukov, Ivan
Fishman, Natalya
Kiryutin, Alexey
Lukzen, Nikita
Panov, Mikhail
Vieth, Hans-Martin
Schäfer, Julian
Lambert, Christoph
Yurkovskaya, Alexandra
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The Journal of Chemical Physics (JCP). American Institute of Physics (AIP). 2020, 152(1), 014203. ISSN 0021-9606. eISSN 1089-7690. Available under: doi: 10.1063/1.5131817
Zusammenfassung

Previous transient absorption measurements using the magnetically affected reaction yield (MARY) technique for a series of rigidly linked electron donor/electron acceptor dyads (D-X-A) consisting of a triarylamine donor, a naphthalene diimide acceptor, and a meta-conjugated diethynylbenzene unit as a bridge had revealed the presence of electronic exchange interaction, J, in the photoexcited charge separated (CS) state. Here, we present results obtained by photochemically induced dynamic nuclear polarization (photo-CIDNP) that allows for determining the sign of J. By variation of the magnetic field from 1 mT to 9.4 T, pronounced absorptive maxima of CIDNP were detected for more than 20 1H nuclei disregarding the sign of their hyperfine coupling constants in the transient charge separated state, with positions of maxima close to those found by the MARY technique. Quantitative comparison of the observed CIDNP signals for various D-X-A dyads reveals an increase in the CIDNP enhancement factor with increasing population of the triplet state determined by MARY spectroscopy at zero magnetic field. For CIDNP of the methyl groups of the TAA donor dyads, we found in all studies a good linear dependence between the CIDNP signal amplitude and the initial population of the CS triplet state. The linear relationship together with the absorptive CIDNP allows us to conclude that (i) the sign of the electronic exchange interaction Jex is positive, (ii) CIDNP is formed predominantly in the vicinity of level anticrossing between the T+ and S electronic levels, and (iii) coherent triplet-singlet transitions are induced by hyperfine interaction and accompanied by simultaneous electron and nuclear spin flip, | | T + β⟩→| | Sα⟩ T+β→Sα .

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ISO 690ZHUKOV, Ivan, Natalya FISHMAN, Alexey KIRYUTIN, Nikita LUKZEN, Mikhail PANOV, Ulrich STEINER, Hans-Martin VIETH, Julian SCHÄFER, Christoph LAMBERT, Alexandra YURKOVSKAYA, 2020. Positive electronic exchange interaction and predominance of minor triplet channel in CIDNP formation in short lived charge separated states of D-X-A dyads. In: The Journal of Chemical Physics (JCP). American Institute of Physics (AIP). 2020, 152(1), 014203. ISSN 0021-9606. eISSN 1089-7690. Available under: doi: 10.1063/1.5131817
BibTex
@article{Zhukov2020-01-07Posit-50088,
  year={2020},
  doi={10.1063/1.5131817},
  title={Positive electronic exchange interaction and predominance of minor triplet channel in CIDNP formation in short lived charge separated states of D-X-A dyads},
  number={1},
  volume={152},
  issn={0021-9606},
  journal={The Journal of Chemical Physics (JCP)},
  author={Zhukov, Ivan and Fishman, Natalya and Kiryutin, Alexey and Lukzen, Nikita and Panov, Mikhail and Steiner, Ulrich and Vieth, Hans-Martin and Schäfer, Julian and Lambert, Christoph and Yurkovskaya, Alexandra},
  note={Article Number: 014203}
}
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