Singlet fission in a hexacene dimer: energetics dictate dynamics

Sanders, Samuel N.; Kumarasamy, Elango; Fallon, Kealan J.; Sfeir, Matthew Y.; Campos, Luis M.

doi:10.1039/c9sc05066c

Title: Singlet fission in a hexacene dimer: energetics dictate dynamics

Journal Article · 08 December 2019 · Chemical Science

DOI: https://doi.org/10.1039/c9sc05066c · OSTI ID:1816620

Sanders, Samuel N. ^[1]; Kumarasamy, Elango ^[2];

^[2];

^[3];

^[2]

Columbia Univ., New York, NY (United States). Dept. of Chemistry; OSTI
Columbia Univ., New York, NY (United States). Dept. of Chemistry
City Univ. of New York (CUNY), NY (United States). Photonics Initiative; City Univ. of New York (CUNY), NY (United States). Graduate Center. Dept. of Physics

Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.

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Sponsoring Organization:: National Science Foundation (NSF); US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1816620

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 4 Vol. 11; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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