Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer
Abstract
The efficiency of an organic solar cell depends on the efficacy of exciton diffusion and dissociation processes, and this can be enhanced by reducing the exciton binding energy and increasing the exciton lifetime. Zinc chlorodipyrrin (ZCl) complexes exhibit reduced exciton binding energy due to ultrafast generation of intramolecular charge transfer (ICT) states via symmetry breaking charge transfer in polar media. This paper explores the fate of the ICT states using nanosecond transient absorption. In cyclohexane, ZCl undergoes intersystem-crossing to produce triplets with ~8 ns time constant (~30% yield) and no ICT states are generated. However, in more polar solvents, triplets are generated within 1 ns via ICT state recombination with ~3 times higher yield than produced via ISC. Furthermore, this high triplet yield in toluene (89%) and acetonitrile (76%) via ICT state recombination is a beneficial pathway to spin-protect the excited state decay for additional charge generation from triplet excited states.
- Publication Date:
- Research Org.:
- Univ. of Southern California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1735856
- Grant/Contract Number:
- SC0016450; CBET-1511757
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Symmetry breaking charge transfer; SBCT; solar fuels; photovoltaic; triplet excited state; zinc dipyrrin; transient absorbance spectroscopy; hydrocarbons; aromatic compounds; solvents; quantum mechanics; recombination
Citation Formats
Das, Saptaparna, Thornbury, William G., Bartynski, Andrew N., Thompson, Mark E., and Bradforth, Stephen E. Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer. United States: N. p., 2018.
Web. doi:10.1021/acs.jpclett.8b01237.
Das, Saptaparna, Thornbury, William G., Bartynski, Andrew N., Thompson, Mark E., & Bradforth, Stephen E. Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer. United States. https://doi.org/10.1021/acs.jpclett.8b01237
Das, Saptaparna, Thornbury, William G., Bartynski, Andrew N., Thompson, Mark E., and Bradforth, Stephen E. Thu .
"Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer". United States. https://doi.org/10.1021/acs.jpclett.8b01237. https://www.osti.gov/servlets/purl/1735856.
@article{osti_1735856,
title = {Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer},
author = {Das, Saptaparna and Thornbury, William G. and Bartynski, Andrew N. and Thompson, Mark E. and Bradforth, Stephen E.},
abstractNote = {The efficiency of an organic solar cell depends on the efficacy of exciton diffusion and dissociation processes, and this can be enhanced by reducing the exciton binding energy and increasing the exciton lifetime. Zinc chlorodipyrrin (ZCl) complexes exhibit reduced exciton binding energy due to ultrafast generation of intramolecular charge transfer (ICT) states via symmetry breaking charge transfer in polar media. This paper explores the fate of the ICT states using nanosecond transient absorption. In cyclohexane, ZCl undergoes intersystem-crossing to produce triplets with ~8 ns time constant (~30% yield) and no ICT states are generated. However, in more polar solvents, triplets are generated within 1 ns via ICT state recombination with ~3 times higher yield than produced via ISC. Furthermore, this high triplet yield in toluene (89%) and acetonitrile (76%) via ICT state recombination is a beneficial pathway to spin-protect the excited state decay for additional charge generation from triplet excited states.},
doi = {10.1021/acs.jpclett.8b01237},
journal = {Journal of Physical Chemistry Letters},
number = 12,
volume = 9,
place = {United States},
year = {Thu May 31 00:00:00 EDT 2018},
month = {Thu May 31 00:00:00 EDT 2018}
}
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