skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Singlet Exciton Fission in Thin Films of tert -Butyl-Substituted Terrylenes

Abstract

Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (tau = 120 +/- 10 ps) and 2 (tau = 320 +/- 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 +/- 20% for 1 and 200 +/- 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1392055
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 18; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Eaton, Samuel W., Miller, Stephen A., Margulies, Eric A., Shoer, Leah E., Schaller, Richard D., and Wasielewski, Michael R. Singlet Exciton Fission in Thin Films of tert -Butyl-Substituted Terrylenes. United States: N. p., 2015. Web. doi:10.1021/acs.jpca.5b02719.
Eaton, Samuel W., Miller, Stephen A., Margulies, Eric A., Shoer, Leah E., Schaller, Richard D., & Wasielewski, Michael R. Singlet Exciton Fission in Thin Films of tert -Butyl-Substituted Terrylenes. United States. doi:10.1021/acs.jpca.5b02719.
Eaton, Samuel W., Miller, Stephen A., Margulies, Eric A., Shoer, Leah E., Schaller, Richard D., and Wasielewski, Michael R. Thu . "Singlet Exciton Fission in Thin Films of tert -Butyl-Substituted Terrylenes". United States. doi:10.1021/acs.jpca.5b02719.
@article{osti_1392055,
title = {Singlet Exciton Fission in Thin Films of tert -Butyl-Substituted Terrylenes},
author = {Eaton, Samuel W. and Miller, Stephen A. and Margulies, Eric A. and Shoer, Leah E. and Schaller, Richard D. and Wasielewski, Michael R.},
abstractNote = {Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (tau = 120 +/- 10 ps) and 2 (tau = 320 +/- 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 +/- 20% for 1 and 200 +/- 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.},
doi = {10.1021/acs.jpca.5b02719},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 18,
volume = 119,
place = {United States},
year = {2015},
month = {5}
}