Tuning the charge transfer character of the multiexciton state in singlet fission
Abstract
Intramolecular singlet fission (SF) produces the multiexciton correlated triplet pair state, (T1T1), prior to the formation of free triplet excitons. The nature of the multiexciton state is complex, as generation of the (T1T1) state may involve a charge transfer (CT) intermediate and has been shown to have both mixed electronic and spin characters. According to transient absorption spectroscopy, a linear terrylene-3,4:11,12-bis(dicarboximide) dimer (TDI2) exhibits solvent-dependent excited-state dynamics. As solvent polarity increases from 1,2,4-trichlorobenzene (ε = 2.2) to chlorobenzene (ε = 5.6) to 1,2-dichlorobenzene (ε = 9.9), the SF rate in TDI2 increases and the multiexciton state, which can be thought of as a linear combination of the 1(S1S0), CT, and (T1T1) states, gains more CT character. Eventually, the CT state becomes a trap state as indicated by symmetry-breaking charge separation in TDI2 in pyridine (ε = 12.3). The dielectric environment influences not only the SF rate and the relative contributions of the 1(S1S0), CT, and (T1T1) states to the overall multiexciton state but also the rate at which the state mixing evolves, with faster dynamics in higher polarity solvents. More importantly, the tunability and presence of strong CT character in the multiexciton state have implications for SF applications since theymore »
- Authors:
-
- Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1800963
- Alternate Identifier(s):
- OSTI ID: 1657625
- Grant/Contract Number:
- FG02-99ER14999
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 153; Journal Issue: 9; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics; 65 Years of Electron Transfer; Dielectric properties; Photoexcitations; Chemical compounds; Emission spectroscopy; Transient-absorption spectroscopy; Fluorescence quantum yield; Excitons; Frequency resolved optical gating; Density functional theory; Time resolved spectroscopy
Citation Formats
Chen, Michelle, Shin, Jae Yoon, Young, Ryan M., and Wasielewski, Michael R. Tuning the charge transfer character of the multiexciton state in singlet fission. United States: N. p., 2020.
Web. doi:10.1063/5.0017919.
Chen, Michelle, Shin, Jae Yoon, Young, Ryan M., & Wasielewski, Michael R. Tuning the charge transfer character of the multiexciton state in singlet fission. United States. https://doi.org/10.1063/5.0017919
Chen, Michelle, Shin, Jae Yoon, Young, Ryan M., and Wasielewski, Michael R. Mon .
"Tuning the charge transfer character of the multiexciton state in singlet fission". United States. https://doi.org/10.1063/5.0017919. https://www.osti.gov/servlets/purl/1800963.
@article{osti_1800963,
title = {Tuning the charge transfer character of the multiexciton state in singlet fission},
author = {Chen, Michelle and Shin, Jae Yoon and Young, Ryan M. and Wasielewski, Michael R.},
abstractNote = {Intramolecular singlet fission (SF) produces the multiexciton correlated triplet pair state, (T1T1), prior to the formation of free triplet excitons. The nature of the multiexciton state is complex, as generation of the (T1T1) state may involve a charge transfer (CT) intermediate and has been shown to have both mixed electronic and spin characters. According to transient absorption spectroscopy, a linear terrylene-3,4:11,12-bis(dicarboximide) dimer (TDI2) exhibits solvent-dependent excited-state dynamics. As solvent polarity increases from 1,2,4-trichlorobenzene (ε = 2.2) to chlorobenzene (ε = 5.6) to 1,2-dichlorobenzene (ε = 9.9), the SF rate in TDI2 increases and the multiexciton state, which can be thought of as a linear combination of the 1(S1S0), CT, and (T1T1) states, gains more CT character. Eventually, the CT state becomes a trap state as indicated by symmetry-breaking charge separation in TDI2 in pyridine (ε = 12.3). The dielectric environment influences not only the SF rate and the relative contributions of the 1(S1S0), CT, and (T1T1) states to the overall multiexciton state but also the rate at which the state mixing evolves, with faster dynamics in higher polarity solvents. More importantly, the tunability and presence of strong CT character in the multiexciton state have implications for SF applications since they often rely on electron transfer from the free triplet excitons. This enhanced CT character in the (T1T1) state may assist with two-electron transfer directly from the (T1T1) state, allowing for facile extraction of charges in intramolecular SF systems whose (T1T1) states do not always efficiently dissociate to two triplet excitons.},
doi = {10.1063/5.0017919},
journal = {Journal of Chemical Physics},
number = 9,
volume = 153,
place = {United States},
year = {Mon Aug 17 00:00:00 EDT 2020},
month = {Mon Aug 17 00:00:00 EDT 2020}
}
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