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Title: Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes

Abstract

Singlet fission (SF) converts a singlet exciton into two triplet excitons in two or more electronically coupled organic chromophores, which may then be used to increase solar cell efficiency. Many known SF chromophores are unsuitable for device applications due to chemical instability or low triplet state energies. The results described here show that efficient SF occurs in derivatives of 9,10-bis(phenylethynyl)anthracene (BPEA), which is a highly robust and tunable chromophore. Fluoro and methoxy substituents at the 4- and 4'-positions of the BPEA phenyl groups control the intermolecular packing in the crystal structure, which alters the interchromophore electronic coupling, while also changing the SF energetics. The lowest excited singlet state (S1) energy of 4,4'-difluoro-BPEA is higher than that of BPEA so that the increased thermodynamic favorability of SF results in a (16 ± 2 ps)-1 SF rate and a 180% ± 16% triplet yield, which is about an order of magnitude faster than BPEA with a comparable triplet yield. By contrast, 4-fluoro-4'-methoxy-BPEA and 4,4'-dimethoxy-BPEA have slower SF rates, (90 ± 20 ps)-1 and (120 ± 10 ps)-1, and lower triplet yields, (110 ± 4)% and (168 ± 7)%, respectively, than 4,4'-difluoro-BPEA. These differences are attributed to changes in the crystal structure controllingmore » interchromophore electronic coupling as well as SF energetics in these polycrystalline solids.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)
OSTI Identifier:
1610423
Alternate Identifier(s):
OSTI ID: 1544909
Grant/Contract Number:  
FG02-99ER14999; SC0001059; FA9550-14-1-0003; ECCS-1542205; DMR-1720139
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 4; 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; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chemistry; physics

Citation Formats

Bae, Youn Jue, Christensen, Joseph A., Kang, Gyeongwon, Zhou, Jiawang, Young, Ryan M., Wu, Yi-Lin, Van Duyne, Richard P., Schatz, George C., and Wasielewski, Michael R. Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes. United States: N. p., 2019. Web. doi:10.1063/1.5110411.
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Bae, Youn Jue, Christensen, Joseph A., Kang, Gyeongwon, Zhou, Jiawang, Young, Ryan M., Wu, Yi-Lin, Van Duyne, Richard P., Schatz, George C., & Wasielewski, Michael R. Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes. United States. https://doi.org/10.1063/1.5110411
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Bae, Youn Jue, Christensen, Joseph A., Kang, Gyeongwon, Zhou, Jiawang, Young, Ryan M., Wu, Yi-Lin, Van Duyne, Richard P., Schatz, George C., and Wasielewski, Michael R. Thu . "Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes". United States. https://doi.org/10.1063/1.5110411. https://www.osti.gov/servlets/purl/1610423.
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@article{osti_1610423,
title = {Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes},
author = {Bae, Youn Jue and Christensen, Joseph A. and Kang, Gyeongwon and Zhou, Jiawang and Young, Ryan M. and Wu, Yi-Lin and Van Duyne, Richard P. and Schatz, George C. and Wasielewski, Michael R.},
abstractNote = {Singlet fission (SF) converts a singlet exciton into two triplet excitons in two or more electronically coupled organic chromophores, which may then be used to increase solar cell efficiency. Many known SF chromophores are unsuitable for device applications due to chemical instability or low triplet state energies. The results described here show that efficient SF occurs in derivatives of 9,10-bis(phenylethynyl)anthracene (BPEA), which is a highly robust and tunable chromophore. Fluoro and methoxy substituents at the 4- and 4'-positions of the BPEA phenyl groups control the intermolecular packing in the crystal structure, which alters the interchromophore electronic coupling, while also changing the SF energetics. The lowest excited singlet state (S1) energy of 4,4'-difluoro-BPEA is higher than that of BPEA so that the increased thermodynamic favorability of SF results in a (16 ± 2 ps)-1 SF rate and a 180% ± 16% triplet yield, which is about an order of magnitude faster than BPEA with a comparable triplet yield. By contrast, 4-fluoro-4'-methoxy-BPEA and 4,4'-dimethoxy-BPEA have slower SF rates, (90 ± 20 ps)-1 and (120 ± 10 ps)-1, and lower triplet yields, (110 ± 4)% and (168 ± 7)%, respectively, than 4,4'-difluoro-BPEA. These differences are attributed to changes in the crystal structure controlling interchromophore electronic coupling as well as SF energetics in these polycrystalline solids.},
doi = {10.1063/1.5110411},
journal = {Journal of Chemical Physics},
number = 4,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}
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https://doi.org/10.1063/1.5110411
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Figures / Tables:

Scheme 1 Scheme 1: The BPEA derivatives used in this study
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    TABLE II (p. 7)table
    FIG. 5 (p. 8)figure
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