Please use this identifier to cite or link to this item: doi:10.22028/D291-29308
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Title: Exploiting Excited-State Aromaticity To Design Highly Stable Singlet Fission Materials
Author(s): Fallon, Kealan J.
Budden, Peter
Salvadori, Enrico
Ganose, Alex M.
Savory, Christopher N.
Eyre, Lissa
Dowland, Simon
Ai, Qianxiang
Goodlett, Stephen
Risko, Chad
Scanlon, David O.
Kay, Christopher
Rao, Akshay
Friend, Richard H.
Musser, Andrew J.
Bronstein, Hugo
Language: English
Title: Journal of the American Chemical Society
Volume: 141
Issue: 35
Startpage: 13867
Endpage: 13876
Publisher/Platform: American Chemical Society (ACS)
Year of Publication: 2019
Publikation type: Journal Article
Abstract: Singlet fission, the process of forming two triplet excitons from one singlet exciton, is a characteristic reserved for only a handful of organic molecules due to the atypical energetic requirement for low energy excited triplet states. The predominant strategy for achieving such a trait is by increasing ground state diradical character; however, this greatly reduces ambient stability. Herein, we exploit Baird's rule of excited state aromaticity to manipulate the singlet-triplet energy gap and create novel singlet fission candidates. We achieve this through the inclusion of a [4n] 5-membered heterocycle, whose electronic resonance promotes aromaticity in the triplet state, stabilizing its energy relative to the singlet excited state. Using this theory, we design a family of derivatives of indolonaphthyridine thiophene (INDT) with highly tunable excited state energies. Not only do we access novel singlet fission materials, they also exhibit excellent ambient stability, imparted due to the delocalized nature of the triplet excited state. Spin-coated films retained up to 85% activity after several weeks of exposure to oxygen and light, while analogous films of TIPS-pentacene showed full degradation after 4 days, showcasing the excellent stability of this class of singlet fission scaffold. Extension of our theoretical analysis to almost ten thousand candidates reveals an unprecedented degree of tunability and several thousand potential fission-capable candidates, while clearly demonstrating the relationship between triplet aromaticity and singlet-triplet energy gap, confirming this novel strategy for manipulating the exchange energy in organic materials.
DOI of the first publication: 10.1021/jacs.9b06346
Link to this record: hdl:20.500.11880/27849
http://dx.doi.org/10.22028/D291-29308
ISSN: 0002-7863
1520-5126
Date of registration: 20-Sep-2019
Faculty: NT - Naturwissenschaftlich- Technische Fakultät
Department: NT - Chemie
Professorship: NT - Prof. Dr. Christopher Kay
Collections:UniBib – Die Universitätsbibliographie

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