Varying the Interpentacene Electronic Coupling to Tune Singlet Fission

Papadopoulos I, Zirzlmeier J, Hetzer C, Bae YJ, Krzyaniak MD, Wasielewski MR, Clark T, Tykwinski R, Guldi DM (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 141

Pages Range: 6191-6203

Journal Issue: 15

DOI: 10.1021/jacs.8b09510

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.

Authors with CRIS profile

Ilias Papadopoulos Lehrstuhl für Physikalische Chemie I Johannes Zirzlmeier Lehrstuhl für Physikalische Chemie I Constantin Hetzer Lehrstuhl für Anorganische und Allgemeine Chemie Timothy Clark Computer-Chemie-Centrum (CCC) Rik Tykwinski Lehrstuhl für Organische Chemie I Dirk Michael Guldi Lehrstuhl für Physikalische Chemie I

Involved external institutions

Northwestern University

United States (USA) (US)

How to cite

APA:

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

MLA:

Papadopoulos, Ilias, et al. "Varying the Interpentacene Electronic Coupling to Tune Singlet Fission." Journal of the American Chemical Society 141.15 (2019): 6191-6203.

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