Excited-State Dynamics of 5,14- vs 6,13-Bis(trialkylsilylethynyl)-Substituted Pentacenes: Implications for Singlet Fission

Ryan D. Pensack, Geoffrey E. Purdum, Samuel M. Mazza, Christopher Grieco, John B. Asbury, John E. Anthony, Yueh Lin Loo, Gregory D. Scholes

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Singlet fission is a process in conjugated organic materials that has the potential to considerably improve the performance of devices in many applications, including solar energy conversion. In any application involving singlet fission, efficient triplet harvesting is essential. At present, not much is known about molecular packing arrangements detrimental to singlet fission. In this work, we report a molecular packing arrangement in crystalline films of 5,14-bis(triisopropylsilylethynyl)-substituted pentacene, specifically a local (pairwise) packing arrangement, responsible for complete quenching of triplet pairs generated via singlet fission. We first demonstrate that the energetic condition necessary for singlet fission is satisfied in amorphous films of the 5,14-substituted pentacene derivative. However, while triplet pairs form highly efficiently in the amorphous films, only a modest yield of independent triplets is observed. In crystalline films, triplet pairs also form highly efficiently, although independent triplets are not observed because triplet pairs decay rapidly and are quenched completely. We assign the quenching to a rapid nonadiabatic transition directly to the ground state. Detrimental quenching is observed in crystalline films of two additional 5,14-bis(trialkylsilylethynyl)-substituted pentacenes with either ethyl or isobutyl substituents. Developing a better understanding of the losses identified in this work, and associated molecular packing, may benefit overcoming losses in solids of other singlet fission materials.

Original languageEnglish
Pages (from-to)9784-9793
Number of pages10
JournalJournal of Physical Chemistry C
Volume126
Issue number23
DOIs
StatePublished - Jun 16 2022

Bibliographical note

Funding Information:
G. D. S., Y.-L. L., R. D. P., and G. E. P acknowledge funding from the Princeton Center for Complex Materials, a MRSEC supported by NSF Grant DMR 1420541. G.D.S. acknowledges partial support for this work from the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant No. DE-SC0015429. Y.-L.L. and G.E.P. acknowledge additional support through NSF Grant DMR 1627453. Portions of this work were conducted at the Cornell High Energy Synchrotron Source (CHESS), which is supported by the NSF and NIH/NIGMS via NSF Award DMR-1332208. J.E.A. and S.M.M. acknowledge funding from the National Science Foundation (DMR 1627428). C.G. and J.B.A. are grateful for support from the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant DE-SC0019349.

Publisher Copyright:
© 2022 American Chemical Society.

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy (all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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