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Parallel triplet formation pathways in a singlet fission material

Author

Listed:
  • Nilabja Maity

    (Indian Institute of Science)

  • Woojae Kim

    (Cornell University
    Yonsei University)

  • Naitik A. Panjwani

    (Freie Universität Berlin)

  • Arup Kundu

    (Tata Institute of Fundamental Research)

  • Kanad Majumder

    (Indian Institute of Science)

  • Pranav Kasetty

    (Indian Institute of Science)

  • Divji Mishra

    (Indian Institute of Science)

  • Robert Bittl

    (Freie Universität Berlin)

  • Jayashree Nagesh

    (Indian Institute of Science)

  • Jyotishman Dasgupta

    (Tata Institute of Fundamental Research)

  • Andrew J. Musser

    (Cornell University)

  • Satish Patil

    (Indian Institute of Science)

Abstract

Harvesting long-lived free triplets in high yields by utilizing organic singlet fission materials can be the cornerstone for increasing photovoltaic efficiencies potentially. However, except for polyacenes, which are the most studied systems in the singlet fission field, spin-entangled correlated triplet pairs and free triplets born through singlet fission are relatively poorly characterized. By utilizing transient absorption and photoluminescence spectroscopy in supramolecular aggregate thin films consisting of Hamilton-receptor-substituted diketopyrrolopyrrole derivatives, we show that photoexcitation gives rise to the formation of spin-0 correlated triplet pair 1(TT) from the lower Frenkel exciton state. The existence of 1(TT) is proved through faint Herzberg-Teller emission that is enabled by vibronic coupling and correlated with an artifact-free triplet-state photoinduced absorption in the near-infrared. Surprisingly, transient electron paramagnetic resonance reveals that long-lived triplets are produced through classical intersystem crossing instead of 1(TT) dissociation, with the two pathways in competition. Moreover, comparison of the triplet-formation dynamics in J-like and H-like thin films with the same energetics reveals that spin-orbit coupling mediated intersystem crossing persists in both. However, 1(TT) only forms in the J-like film, pinpointing the huge impact of intermolecular coupling geometry on singlet fission dynamics.

Suggested Citation

  • Nilabja Maity & Woojae Kim & Naitik A. Panjwani & Arup Kundu & Kanad Majumder & Pranav Kasetty & Divji Mishra & Robert Bittl & Jayashree Nagesh & Jyotishman Dasgupta & Andrew J. Musser & Satish Patil, 2022. "Parallel triplet formation pathways in a singlet fission material," Nature Communications, Nature, vol. 13(1), pages 1-14, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-32844-6
    DOI: 10.1038/s41467-022-32844-6
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    References listed on IDEAS

    as
    1. Jiahua Hu & Ke Xu & Lei Shen & Qin Wu & Guiying He & Jie-Yu Wang & Jian Pei & Jianlong Xia & Matthew Y. Sfeir, 2018. "New insights into the design of conjugated polymers for intramolecular singlet fission," Nature Communications, Nature, vol. 9(1), pages 1-9, December.
    2. K. C. Krishnapriya & Palas Roy & Boregowda Puttaraju & Ulrike Salzner & Andrew J. Musser & Manish Jain & Jyotishman Dasgupta & Satish Patil, 2019. "Spin density encodes intramolecular singlet exciton fission in pentacene dimers," Nature Communications, Nature, vol. 10(1), pages 1-8, December.
    3. Christoph Schnedermann & Antonios M. Alvertis & Torsten Wende & Steven Lukman & Jiaqi Feng & Florian A. Y. N. Schröder & David H. P. Turban & Jishan Wu & Nicholas D. M. Hine & Neil C. Greenham & Alex , 2019. "A molecular movie of ultrafast singlet fission," Nature Communications, Nature, vol. 10(1), pages 1-11, December.
    4. Chaw Keong Yong & Andrew J. Musser & Sam L. Bayliss & Steven Lukman & Hiroyuki Tamura & Olga Bubnova & Rawad K. Hallani & Aurélie Meneau & Roland Resel & Munetaka Maruyama & Shu Hotta & Laura M. Herz , 2017. "The entangled triplet pair state in acene and heteroacene materials," Nature Communications, Nature, vol. 8(1), pages 1-12, August.
    5. Steven Lukman & Kai Chen & Justin M. Hodgkiss & David H. P. Turban & Nicholas D. M. Hine & Shaoqiang Dong & Jishan Wu & Neil C. Greenham & Andrew J. Musser, 2016. "Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering," Nature Communications, Nature, vol. 7(1), pages 1-13, December.
    6. Daphné Lubert-Perquel & Enrico Salvadori & Matthew Dyson & Paul N. Stavrinou & Riccardo Montis & Hiroki Nagashima & Yasuhiro Kobori & Sandrine Heutz & Christopher W. M. Kay, 2018. "Identifying triplet pathways in dilute pentacene films," Nature Communications, Nature, vol. 9(1), pages 1-10, December.
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