Varying the Interpentacene Electronic Coupling to Tune Singlet Fission

Ilias Papadopoulos, Johannes Zirzlmeier, Constantin Hetzer, Youn J. Bae, Matthew D. Krzyaniak, Michael R Wasielewski, Timothy Clark, Rik R. Tykwinski, Dirk M. Guldi

Research output: Contribution to journalArticle

Abstract

We have designed and used four different spacers, denoted A-D, to connect two pentacenes and to probe the impact of intramolecular forces on the modulation of pentacene-pentacene interactions and, in turn, on the key steps in singlet fission (SF), that is, the 1 (S 1 S 0 )-to- 1 (T 1 T 1 ) as well as 1 (T 1 T 1 )-to- 5 (T 1 T 1 ) transitions by means of transient absorption and electron paramagnetic resonance measurements. In terms of the 1 (S 1 S 0 )-to- 1 (T 1 T 1 ) transition, a superexchange mechanism, that is, coupling to a higher-lying CT state to generate a virtual intermediate, enables rapid SF in A-D. Sizeable electronic coupling in A and B opens, on one hand, an additional pathway, that is, the population of a real intermediate, and changes, on the other hand, the mechanism to that of hopping. In turn, A and B feature much higher 1 (T 1 T 1 ) quantum yields than C and D, with a maximum value of 162% for A. In terms of the 1 (T 1 T 1 )-to- 5 (T 1 T 1 ) transition, the sizable electronic coupling in A and B is counterproductive, and C and D give rise to higher 5 (T 1 T 1 )-to-(T 1 + T 1 ) quantum yields than A and B, with a maximum value of 85% for D.

Original languageEnglish
Pages (from-to)6191-6203
Number of pages13
JournalJournal of the American Chemical Society
Volume141
Issue number15
DOIs
Publication statusPublished - Apr 17 2019

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Quantum yield
Electron Spin Resonance Spectroscopy
Paramagnetic resonance
Modulation
Population
pentacene

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Papadopoulos, I., Zirzlmeier, J., Hetzer, C., Bae, Y. J., Krzyaniak, M. D., Wasielewski, M. R., ... Guldi, D. M. (2019). Varying the Interpentacene Electronic Coupling to Tune Singlet Fission. Journal of the American Chemical Society, 141(15), 6191-6203. https://doi.org/10.1021/jacs.8b09510

Varying the Interpentacene Electronic Coupling to Tune Singlet Fission. / Papadopoulos, Ilias; Zirzlmeier, Johannes; Hetzer, Constantin; Bae, Youn J.; Krzyaniak, Matthew D.; Wasielewski, Michael R; Clark, Timothy; Tykwinski, Rik R.; Guldi, Dirk M.

In: Journal of the American Chemical Society, Vol. 141, No. 15, 17.04.2019, p. 6191-6203.

Research output: Contribution to journalArticle

Papadopoulos, I, Zirzlmeier, J, Hetzer, C, Bae, YJ, Krzyaniak, MD, Wasielewski, MR, Clark, T, Tykwinski, RR & Guldi, DM 2019, 'Varying the Interpentacene Electronic Coupling to Tune Singlet Fission', Journal of the American Chemical Society, vol. 141, no. 15, pp. 6191-6203. https://doi.org/10.1021/jacs.8b09510
Papadopoulos, Ilias ; Zirzlmeier, Johannes ; Hetzer, Constantin ; Bae, Youn J. ; Krzyaniak, Matthew D. ; Wasielewski, Michael R ; Clark, Timothy ; Tykwinski, Rik R. ; Guldi, Dirk M. / Varying the Interpentacene Electronic Coupling to Tune Singlet Fission. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 15. pp. 6191-6203.
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