Varying the Interpentacene Electronic Coupling to Tune Singlet Fission

Journal article


Publication Details

Author(s): Papadopoulos I, Zirzlmeier J, Hetzer C, Bae YJ, Krzyaniak MD, Wasielewski MR, Clark T, Tykwinski R, Guldi DM
Journal: Journal of the American Chemical Society
Publication year: 2019
Volume: 141
Journal issue: 15
Pages range: 6191-6203
ISSN: 1520-5126


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.


FAU Authors / FAU Editors

Clark, Timothy apl. Prof. Dr.
Computer-Chemie-Centrum
Guldi, Dirk Michael Prof. Dr.
Lehrstuhl für Physikalische Chemie I
Hetzer, Constantin
Lehrstuhl für Anorganische und Allgemeine Chemie
Papadopoulos, Ilias
Lehrstuhl für Physikalische Chemie I
Tykwinski, Rik Prof.
Lehrstuhl für Organische Chemie I
Zirzlmeier, Johannes
Lehrstuhl für Physikalische Chemie I


External institutions with authors

Northwestern University


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://dx.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.

BibTeX: 

Last updated on 2019-14-05 at 21:08