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

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.

doi:10.1063/1.5110411

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

Journal Article · 25 July 2019 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5110411 · OSTI ID:1610423

^[1]; Christensen, Joseph A. ^[1];

^[1];

^[1]; Young, Ryan M. ^[1];

^[1]; Van Duyne, Richard P. ^[1];

^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)

Grant/Contract Number:: FG02-99ER14999; SC0001059; FA9550-14-1-0003; ECCS-1542205; DMR-1720139

OSTI ID:: 1610423

Alternate ID(s):: OSTI ID: 1544909

Journal Information:: Journal of Chemical Physics, Vol. 151, Issue 4; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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CCDC 1907242: Experimental Crystal Structure Determination Jue, Bae, Youn; A., Christensen, Joseph; Gyeongwon, Kang, https://doi.org/10.5517/ccdc.csd.cc220myp The current record is supplemented by this dataset	dataset	January 2019
CCDC 1909837: Experimental Crystal Structure Determination Jue, Bae, Youn; A., Christensen, Joseph; Gyeongwon, Kang, https://doi.org/10.5517/ccdc.csd.cc223bn6 The current record is supplemented by this dataset	dataset	January 2019