Harnessing Molecular Vibrations to Probe Triplet Dynamics during Singlet Fission

Christopher Grieco; Eric R. Kennehan; Adam Rimshaw; Marcia M. Payne; John E. Anthony; John B. Asbury

doi:10.1021/acs.jpclett.7b02434

Harnessing Molecular Vibrations to Probe Triplet Dynamics during Singlet Fission

Christopher Grieco
, Eric R. Kennehan
, Adam Rimshaw
, Marcia M. Payne
, John E. Anthony
, John B. Asbury

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

42 Scopus citations

Abstract

Ultrafast vibrational spectroscopy in the mid-infrared spectral range provides the opportunity to probe the dynamics of electronic states involved in all stages of the singlet fission reaction through their unique vibrational frequencies. This capability is demonstrated using a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). The alkyne groups of the TIPS side chains are coupled to the conjugated framework of the pentacene cores, enabling direct examination of the dynamics of triplet excitons that have successfully separated from correlated triplet pair states in crystalline films of TIPS-Pn. Relaxation processes during the separation of triplet excitons and triplet-triplet annihilation after their separation result in the formation of hot ground state molecules that also exhibit unique vibrational frequencies. Because all organic molecules possess native vibrational modes, ultrafast vibrational spectroscopy offers a new approach to examine the dynamics of electronic intermediates that may inform ongoing efforts to utilize singlet fission to overcome thermalization losses in photovoltaic applications.

Original language	English
Pages (from-to)	5700-5706
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	8
Issue number	23
DOIs	https://doi.org/10.1021/acs.jpclett.7b02434
State	Published - Dec 7 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

Funding

C.G., E.R.K., A.R., and J.B.A. thank the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant DE-SC0008120 for support of this research. J.E.A. and M.M.P. thank the National Science Foundation (CMMI-1255494) for support of organic semiconductor synthesis. C.G., E.R.K., A.R., and J.B.A. thank the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant DESC0008120 for support of this research. J.E.A. and M.M.P. thank the National Science Foundation (CMMI-1255494) for support of organic semiconductor synthesis.

Funders	Funder number
Office of Basic Energy Sciences
National Science Foundation (NSF)	CMMI-1255494
Michigan State University-U.S. Department of Energy (MSU-DOE) Plant Research Laboratory	DESC0008120
Chemical Sciences, Geosciences, and Biosciences Division
National Science Foundation (NSF)

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

ASJC Scopus subject areas

General Materials Science
Physical and Theoretical Chemistry

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10.1021/acs.jpclett.7b02434

Cite this

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title = "Harnessing Molecular Vibrations to Probe Triplet Dynamics during Singlet Fission",

abstract = "Ultrafast vibrational spectroscopy in the mid-infrared spectral range provides the opportunity to probe the dynamics of electronic states involved in all stages of the singlet fission reaction through their unique vibrational frequencies. This capability is demonstrated using a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). The alkyne groups of the TIPS side chains are coupled to the conjugated framework of the pentacene cores, enabling direct examination of the dynamics of triplet excitons that have successfully separated from correlated triplet pair states in crystalline films of TIPS-Pn. Relaxation processes during the separation of triplet excitons and triplet-triplet annihilation after their separation result in the formation of hot ground state molecules that also exhibit unique vibrational frequencies. Because all organic molecules possess native vibrational modes, ultrafast vibrational spectroscopy offers a new approach to examine the dynamics of electronic intermediates that may inform ongoing efforts to utilize singlet fission to overcome thermalization losses in photovoltaic applications.",

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AU - Payne, Marcia M.

AU - Anthony, John E.

AU - Asbury, John B.

PY - 2017/12/7

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AB - Ultrafast vibrational spectroscopy in the mid-infrared spectral range provides the opportunity to probe the dynamics of electronic states involved in all stages of the singlet fission reaction through their unique vibrational frequencies. This capability is demonstrated using a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). The alkyne groups of the TIPS side chains are coupled to the conjugated framework of the pentacene cores, enabling direct examination of the dynamics of triplet excitons that have successfully separated from correlated triplet pair states in crystalline films of TIPS-Pn. Relaxation processes during the separation of triplet excitons and triplet-triplet annihilation after their separation result in the formation of hot ground state molecules that also exhibit unique vibrational frequencies. Because all organic molecules possess native vibrational modes, ultrafast vibrational spectroscopy offers a new approach to examine the dynamics of electronic intermediates that may inform ongoing efforts to utilize singlet fission to overcome thermalization losses in photovoltaic applications.

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Harnessing Molecular Vibrations to Probe Triplet Dynamics during Singlet Fission

Abstract

Bibliographical note

Funding

UN SDGs

ASJC Scopus subject areas

Access to Document

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