The influence of hindered rotation on electron transfer and exchange interaction in triarylamine-triptycene-perylene diimide triads

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2024
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Roger, Chantal
Schmiedel, Alexander
Holzapfel, Marco
Lukzen, Nikita N.
Lambert, Christoph
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Physical Chemistry Chemical Physics. Royal Society of Chemistry (RSC). 2024, 26(6), pp. 4954-4967. ISSN 1463-9084. eISSN 1463-9076. Available under: doi: 10.1039/D3CP05785B
Zusammenfassung

Stretched electron-donor-bridge-acceptor triads that exhibit intramolecular twisting degrees of freedom are capable of modulating exchange interaction (J) as well as electronic couplings through variable π-overlap at the linear bond links, affecting the rate constants of photoinduced charge separation and recombination. Here we present an in-depth investigation of such effects induced by methyl substituents leading to controlled steric hindrance of intramolecular twisting around biaryl axes. Starting from the parent structure, consisting of a triphenyl amine donor, a triptycene (TTC) bridge and a phenylene-perylene diimide acceptor (Me0), one of the two phenylene linkers attached to the TTC was ortho-substituted by two methyl groups (Me2, Me3), or both such phenylene linkers by two pairs of methyl groups (Me23). Photoinduced charge separation (kCS) leading to a charge-separated (CS) state was studied by fs-laser spectroscopy, charge recombination to either singlet ground state (kS) or to the first excited local triplet state of the acceptor (kT) by ns-laser spectroscopy, whereby kinetic magnetic field effects in an external magnetic field were recorded and analysed using quantum dynamic simulations of the spin dependent kinetics of the CS state. Kinetic spectra of the initial first order rate constants of charge recombination (k(B)) exhibited characteristic J-resonances progressing to lower fields in the series Me0, Me2, Me3, Me23. From the quantum simulations, the values of the parameters J, kS, kT and kSTD, the singlet/triplet dephasing constant, were obtained. They were analysed in terms of molecular dynamics simulations of the intramolecular twisting dynamics based on potentials calculated by density functional theory. Apart from kT, all of the parameters exhibit a clear correlation with the averaged cosine square products of the biaryl angles.

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540 Chemie
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Photo electron transfer, spin chemistry, exchange interaction, electronic coupling
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ISO 690ROGER, Chantal, Alexander SCHMIEDEL, Marco HOLZAPFEL, Nikita N. LUKZEN, Ulrich STEINER, Christoph LAMBERT, 2024. The influence of hindered rotation on electron transfer and exchange interaction in triarylamine-triptycene-perylene diimide triads. In: Physical Chemistry Chemical Physics. Royal Society of Chemistry (RSC). 2024, 26(6), pp. 4954-4967. ISSN 1463-9084. eISSN 1463-9076. Available under: doi: 10.1039/D3CP05785B
BibTex
@article{Roger2024influ-69193,
  year={2024},
  doi={10.1039/D3CP05785B},
  title={The influence of hindered rotation on electron transfer and exchange interaction in triarylamine-triptycene-perylene diimide triads},
  number={6},
  volume={26},
  issn={1463-9084},
  journal={Physical Chemistry Chemical Physics},
  pages={4954--4967},
  author={Roger, Chantal and Schmiedel, Alexander and Holzapfel, Marco and Lukzen, Nikita N. and Steiner, Ulrich and Lambert, Christoph}
}
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