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 language | English |
|---|---|
| Pages (from-to) | 6191-6203 |
| Number of pages | 13 |
| Journal | Journal of the American Chemical Society |
| Volume | 141 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - Apr 17 2019 |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
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 journal › Article
}
TY - JOUR
T1 - Varying the Interpentacene Electronic Coupling to Tune Singlet Fission
AU - Papadopoulos, Ilias
AU - Zirzlmeier, Johannes
AU - Hetzer, Constantin
AU - Bae, Youn J.
AU - Krzyaniak, Matthew D.
AU - Wasielewski, Michael R
AU - Clark, Timothy
AU - Tykwinski, Rik R.
AU - Guldi, Dirk M.
PY - 2019/4/17
Y1 - 2019/4/17
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.8b09510
DO - 10.1021/jacs.8b09510
M3 - Article
VL - 141
SP - 6191
EP - 6203
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 15
ER -