Abstract
Cyano-substituted tetracenes (5,11-dicyano-6,12-diphenyltetracene, Tet) undergo exoergic singlet fission (SF), a spin-allowed photophysical process that generates a pair of triplet excitons from one singlet exciton. To elucidate substituent effects on SF, we have measured the SF dynamics and triplet yields of thin films, formed by Tet bearing hydrogen (H), methyl (Me), fluoro (F), and trimethylsilyl (TMS) substituents on the p-phenyl positions and on the 3 and 9 positions of the tetracene core, by time-resolved spectroscopy in the vis-NIR and IR regions. The H-, Me-, and F-Tet display strong intramolecular electronic coupling (π-π distances <4 Å), and SF gives high triplet exciton yields up to 200% (quantitative). In addition, a charge-transfer state mediates SF in F-Tet films, while H-Tet and Me-Tet show no evidence for such a state. Correlations between the SF yields and the crystal structure show that chromophore slippage along both their short and long axes allows efficient SF and that a large degree of π contact between the chromophores is not necessary for rapid and efficient SF in the solid state. As expected, the large interchromophore distance in TMS-Tet (>4 Å) reduces its SF triplet yield to about 60%.
| Original language | English |
|---|---|
| Pages (from-to) | 21262-21271 |
| Number of pages | 10 |
| Journal | Journal of Physical Chemistry C |
| Volume | 121 |
| Issue number | 39 |
| DOIs | |
| Publication status | Published - Jan 1 2017 |
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ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Energy(all)
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
Cite this
Substituent effects on singlet exciton fission in polycrystalline thin films of Cyano-substituted diaryltetracenes. / Margulies, Eric A.; Kerisit, Nicolas; Gawel, Przemyslaw; Mauck, Catherine M.; Ma, Lin; Miller, Claire E.; Young, Ryan M.; Trapp, Nils; Wu, Yi Lin; Diederich, Francois; Wasielewski, Michael R.
In: Journal of Physical Chemistry C, Vol. 121, No. 39, 01.01.2017, p. 21262-21271.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Substituent effects on singlet exciton fission in polycrystalline thin films of Cyano-substituted diaryltetracenes
AU - Margulies, Eric A.
AU - Kerisit, Nicolas
AU - Gawel, Przemyslaw
AU - Mauck, Catherine M.
AU - Ma, Lin
AU - Miller, Claire E.
AU - Young, Ryan M.
AU - Trapp, Nils
AU - Wu, Yi Lin
AU - Diederich, Francois
AU - Wasielewski, Michael R
PY - 2017/1/1
Y1 - 2017/1/1
N2 - Cyano-substituted tetracenes (5,11-dicyano-6,12-diphenyltetracene, Tet) undergo exoergic singlet fission (SF), a spin-allowed photophysical process that generates a pair of triplet excitons from one singlet exciton. To elucidate substituent effects on SF, we have measured the SF dynamics and triplet yields of thin films, formed by Tet bearing hydrogen (H), methyl (Me), fluoro (F), and trimethylsilyl (TMS) substituents on the p-phenyl positions and on the 3 and 9 positions of the tetracene core, by time-resolved spectroscopy in the vis-NIR and IR regions. The H-, Me-, and F-Tet display strong intramolecular electronic coupling (π-π distances <4 Å), and SF gives high triplet exciton yields up to 200% (quantitative). In addition, a charge-transfer state mediates SF in F-Tet films, while H-Tet and Me-Tet show no evidence for such a state. Correlations between the SF yields and the crystal structure show that chromophore slippage along both their short and long axes allows efficient SF and that a large degree of π contact between the chromophores is not necessary for rapid and efficient SF in the solid state. As expected, the large interchromophore distance in TMS-Tet (>4 Å) reduces its SF triplet yield to about 60%.
AB - Cyano-substituted tetracenes (5,11-dicyano-6,12-diphenyltetracene, Tet) undergo exoergic singlet fission (SF), a spin-allowed photophysical process that generates a pair of triplet excitons from one singlet exciton. To elucidate substituent effects on SF, we have measured the SF dynamics and triplet yields of thin films, formed by Tet bearing hydrogen (H), methyl (Me), fluoro (F), and trimethylsilyl (TMS) substituents on the p-phenyl positions and on the 3 and 9 positions of the tetracene core, by time-resolved spectroscopy in the vis-NIR and IR regions. The H-, Me-, and F-Tet display strong intramolecular electronic coupling (π-π distances <4 Å), and SF gives high triplet exciton yields up to 200% (quantitative). In addition, a charge-transfer state mediates SF in F-Tet films, while H-Tet and Me-Tet show no evidence for such a state. Correlations between the SF yields and the crystal structure show that chromophore slippage along both their short and long axes allows efficient SF and that a large degree of π contact between the chromophores is not necessary for rapid and efficient SF in the solid state. As expected, the large interchromophore distance in TMS-Tet (>4 Å) reduces its SF triplet yield to about 60%.
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U2 - 10.1021/acs.jpcc.7b07870
DO - 10.1021/acs.jpcc.7b07870
M3 - Article
AN - SCOPUS:85032841270
VL - 121
SP - 21262
EP - 21271
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 39
ER -