Singlet fission and triplet pair recombination in bipentacenes with a twist

Yablon, Lauren M.; Sanders, Samuel N.; Miyazaki, Ken; Kumarasamy, Elango; He, Guiying; Choi, Bonnie; Ananth, Nandini; Sfeir, Matthew Y.; Campos, Luis M.

doi:10.1039/d1mh01201k

Singlet fission and triplet pair recombination in bipentacenes with a twist

Journal Article · Fri Oct 22 00:00:00 EDT 2021 · Materials Horizons

DOI:https://doi.org/10.1039/d1mh01201k· OSTI ID:1865051

Yablon, Lauren M. ^[1]; Sanders, Samuel N. ^[2]; ^[3]; Kumarasamy, Elango ^[2]; He, Guiying ^[4]; Choi, Bonnie ^[2]; Ananth, Nandini ^[3]; ^[4]; ^[2]

Columbia Univ., New York, NY (United States); City University of New York
Columbia Univ., New York, NY (United States)
Cornell Univ., Ithaca, NY (United States)
City Univ. of New York, NY (United States)

We investigate triplet pair dynamics in pentacene dimers that have varying degrees of coplanarity (pentacene–pentacene twist angle). The fine-tuning of the twist angle was achieved by alternating connectivity at the 1-position or 2-positions of pentacene. This mix-and-match connectivity leads to tunable twist angles between the two covalently linked pentacenes. These twisted dimers allow us to investigate the subtle effects that the dihedral angle between the covalently linked pentacenes imparts on singlet fission and triplet pair recombination dynamics. We observe that as the dihedral angle between the two bonded pentacenes is increased, the rates of singlet fission decrease, while the accompanying decrease in triplet recombination rates is stark. Temperature-dependent transient optical studies combined with theoretical calculations show that the triplet pair recombination proceeds primarily through a direct multiexciton internal conversion process. Calculations further show that the significant decrease in recombination rates can be directly attributed to a corresponding decrease in the magnitude of the nonadiabatic coupling between the singlet multiexcitonic state and the ground state. Furthermore, these results highlight the importance of the twist angle in designing systems that exhibit rapid singlet fission, while maintaining long triplet pair lifetimes in pentacene dimers.

View Accepted Manuscript (DOE)

Research Organization:: City Univ. of New York, NY (United States); Columbia Univ., New York, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0022036

OSTI ID:: 1865051

Alternate ID(s):: OSTI ID: 1833103

Journal Information:: Materials Horizons, Journal Name: Materials Horizons Journal Issue: 1 Vol. 9; ISSN 2051-6347

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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