Vibrational probe of the origin of singlet exciton fission in TIPS-pentacene solutions

Grieco, Christopher; Doucette, Grayson S.; Munson, Kyle T.; Swartzfager, John R.; Munro, Jason M.; Anthony, John E.; Dabo, Ismaila; Asbury, John B.

doi:10.1063/1.5116586

Vibrational probe of the origin of singlet exciton fission in TIPS-pentacene solutions

Journal Article · Tue Oct 15 00:00:00 EDT 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5116586· OSTI ID:1803718

Grieco, Christopher ^[1]; Doucette, Grayson S. ^[2]; Munson, Kyle T. ^[3]; Swartzfager, John R. ^[3]; Munro, Jason M. ^[4]; Anthony, John E. ^[5]; ^[4]; ^[6]

Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry; OSTI
Pennsylvania State Univ., University Park, PA (United States). Intercollege Materials Science and Engineering Program. Dept. of Materials Science and Engineering
Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry
Pennsylvania State Univ., University Park, PA (United States). Dept. of Materials Science and Engineering
Univ. of Kentucky, Lexington, KY (United States). Dept. of Chemistry
Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry. Intercollege Materials Science and Engineering Program

We use native vibrational modes of the model singlet fission chromophore 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) to examine the origins of singlet fission in solution between molecules that are not tethered by a covalent linkage. We use the C—H stretch modes of TIPS side groups of TIPS-Pn to demonstrate that singlet fission does not occur by diffusive encounter of independent molecules in solution. Instead, TIPS-Pn molecules aggregate in solution through their TIPS side groups. This aggregation breaks the symmetry of the TIPS-Pn molecules and enables the formation of triplets to be probed through the formally symmetry forbidden symmetric alkyne stretch mode of the TIPS side groups. The alkyne stretch modes of TIPS-Pn are sensitive to the electronic excited states present during the singlet fission reaction and provide unique signatures of the formation of triplets following the initial separation of triplet pair intermediates. These findings highlight the opportunity to leverage structural information from vibrational modes to better understand intermolecular interactions that lead to singlet fission.

View Accepted Manuscript (DOE)

Research Organization:: Pennsylvania State Univ., University Park, PA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019349

OSTI ID:: 1803718

Alternate ID(s):: OSTI ID: 1839367
OSTI ID: 1570495

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 15 Vol. 151; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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