Near-Infrared Absorption Features of Triplet-Pair States Assigned by Photoinduced-Absorption-Detected Magnetic Resonance

Ryan D. Dill; Gajadhar Joshi; Karl J. Thorley; John E. Anthony; Brian Fluegel; Justin C. Johnson; Obadiah G. Reid

doi:10.1021/acs.jpclett.2c03665

Near-Infrared Absorption Features of Triplet-Pair States Assigned by Photoinduced-Absorption-Detected Magnetic Resonance

Ryan D. Dill, Gajadhar Joshi, Karl J. Thorley, John E. Anthony, Brian Fluegel, Justin C. Johnson, Obadiah G. Reid

Research output: Contribution to journal › Article › peer-review

Abstract

Singlet fission proceeds through a manifold of triplet-pair states that are exceedingly difficult to distinguish spectroscopically. Here, we introduce a new implementation of photoinduced-absorption-detected magnetic resonance (PADMR) and use it to understand the excited-state absorption spectrum of a tri-2-pentylsilylethynyl pentadithiophene (TSPS-PDT) film. These experiments allow us to directly correlate magnetic transitions driven by RF with electronic transitions in the visible and near-infrared spectrum with high sensitivity. We find that the new near-infrared excited-state transitions that arise in thin films of TSPS-PDT are correlated with the magnetic transitions of T₁, not ⁵TT. Thus, we assign these features to the excited-state absorption of ¹TT, which is depleted when T₁ states are driven to a spin configuration that forbids subsequent fusion. These results clarify the disputed origin of triplet-associated near-infrared absorption features in singlet-fission materials and demonstrate an incisive general purpose tool for studying the evolution of high-spin excited states.

Original language	English
Pages (from-to)	2387-2394
Number of pages	8
Journal	Journal of Physical Chemistry Letters
Volume	14
Issue number	9
DOIs	https://doi.org/10.1021/acs.jpclett.2c03665
State	Published - Mar 9 2023

Bibliographical note

Funding Information:
This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding was provided by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

ASJC Scopus subject areas

Materials Science (all)
Physical and Theoretical Chemistry

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10.1021/acs.jpclett.2c03665

Cite this

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title = "Near-Infrared Absorption Features of Triplet-Pair States Assigned by Photoinduced-Absorption-Detected Magnetic Resonance",

abstract = "Singlet fission proceeds through a manifold of triplet-pair states that are exceedingly difficult to distinguish spectroscopically. Here, we introduce a new implementation of photoinduced-absorption-detected magnetic resonance (PADMR) and use it to understand the excited-state absorption spectrum of a tri-2-pentylsilylethynyl pentadithiophene (TSPS-PDT) film. These experiments allow us to directly correlate magnetic transitions driven by RF with electronic transitions in the visible and near-infrared spectrum with high sensitivity. We find that the new near-infrared excited-state transitions that arise in thin films of TSPS-PDT are correlated with the magnetic transitions of T1, not 5TT. Thus, we assign these features to the excited-state absorption of 1TT, which is depleted when T1 states are driven to a spin configuration that forbids subsequent fusion. These results clarify the disputed origin of triplet-associated near-infrared absorption features in singlet-fission materials and demonstrate an incisive general purpose tool for studying the evolution of high-spin excited states.",

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note = "Funding Information: This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding was provided by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

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N2 - Singlet fission proceeds through a manifold of triplet-pair states that are exceedingly difficult to distinguish spectroscopically. Here, we introduce a new implementation of photoinduced-absorption-detected magnetic resonance (PADMR) and use it to understand the excited-state absorption spectrum of a tri-2-pentylsilylethynyl pentadithiophene (TSPS-PDT) film. These experiments allow us to directly correlate magnetic transitions driven by RF with electronic transitions in the visible and near-infrared spectrum with high sensitivity. We find that the new near-infrared excited-state transitions that arise in thin films of TSPS-PDT are correlated with the magnetic transitions of T1, not 5TT. Thus, we assign these features to the excited-state absorption of 1TT, which is depleted when T1 states are driven to a spin configuration that forbids subsequent fusion. These results clarify the disputed origin of triplet-associated near-infrared absorption features in singlet-fission materials and demonstrate an incisive general purpose tool for studying the evolution of high-spin excited states.

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Near-Infrared Absorption Features of Triplet-Pair States Assigned by Photoinduced-Absorption-Detected Magnetic Resonance

Abstract

Bibliographical note

ASJC Scopus subject areas

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