Two-Dimensional Electronic Spectroscopy Reveals Excitation Energy-Dependent State Mixing during Singlet Fission in a Terrylenediimide Dimer

Aritra Mandal, Michelle Chen, Eileen D. Foszcz, Jonathan D. Schultz, Nicholas M. Kearns, Ryan M. Young, Martin T. Zanni, Michael R Wasielewski

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Singlet fission (SF) is a spin-allowed process in which a singlet exciton, 1(S1S0), within an assembly of two or more chromophores spontaneously down-converts into two triplet excitons via a multiexciton correlated triplet pair state, 1(T1T1). To elucidate the involvement of charge transfer (CT) states and vibronic coupling in SF, we performed 2D electronic spectroscopy (2DES) on dilute solutions of a covalently linked, slip-stacked terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer. This dimer undergoes efficient SF in nonpolar 1,4-dioxane and symmetry-breaking charge separation in polar dichloromethane. The various 2DES spectral features in 1,4-dioxane show different pump wavelength dependencies, supporting the presence of mixed states with variable 1(S1S0), 1(T1T1) and CT contributions that evolve with time. Analysis of the 2DES spectra in dichloromethane reveals the presence of a state having largely 1(T1T1) character during charge separation. Therefore, the 1(T1T1) multiexciton state plays an important role in the photophysics of this TDI dimer irrespective of solvent polarity.

Original languageEnglish
JournalJournal of the American Chemical Society
DOIs
Publication statusAccepted/In press - Jan 1 2018

Fingerprint

Excitation energy
Dimers
Spectrum Analysis
Methylene Chloride
Dichloromethane
Spectroscopy
Excitons
Charge transfer
Chromophores
Pumps
Wavelength
LDS 751
1,4-dioxane

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Two-Dimensional Electronic Spectroscopy Reveals Excitation Energy-Dependent State Mixing during Singlet Fission in a Terrylenediimide Dimer. / Mandal, Aritra; Chen, Michelle; Foszcz, Eileen D.; Schultz, Jonathan D.; Kearns, Nicholas M.; Young, Ryan M.; Zanni, Martin T.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, 01.01.2018.

Research output: Contribution to journalArticle

Mandal, Aritra ; Chen, Michelle ; Foszcz, Eileen D. ; Schultz, Jonathan D. ; Kearns, Nicholas M. ; Young, Ryan M. ; Zanni, Martin T. ; Wasielewski, Michael R. / Two-Dimensional Electronic Spectroscopy Reveals Excitation Energy-Dependent State Mixing during Singlet Fission in a Terrylenediimide Dimer. In: Journal of the American Chemical Society. 2018.
@article{21c0b40dee6b494d986f492bbaa0ec4c,
title = "Two-Dimensional Electronic Spectroscopy Reveals Excitation Energy-Dependent State Mixing during Singlet Fission in a Terrylenediimide Dimer",
abstract = "Singlet fission (SF) is a spin-allowed process in which a singlet exciton, 1(S1S0), within an assembly of two or more chromophores spontaneously down-converts into two triplet excitons via a multiexciton correlated triplet pair state, 1(T1T1). To elucidate the involvement of charge transfer (CT) states and vibronic coupling in SF, we performed 2D electronic spectroscopy (2DES) on dilute solutions of a covalently linked, slip-stacked terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer. This dimer undergoes efficient SF in nonpolar 1,4-dioxane and symmetry-breaking charge separation in polar dichloromethane. The various 2DES spectral features in 1,4-dioxane show different pump wavelength dependencies, supporting the presence of mixed states with variable 1(S1S0), 1(T1T1) and CT contributions that evolve with time. Analysis of the 2DES spectra in dichloromethane reveals the presence of a state having largely 1(T1T1) character during charge separation. Therefore, the 1(T1T1) multiexciton state plays an important role in the photophysics of this TDI dimer irrespective of solvent polarity.",
author = "Aritra Mandal and Michelle Chen and Foszcz, {Eileen D.} and Schultz, {Jonathan D.} and Kearns, {Nicholas M.} and Young, {Ryan M.} and Zanni, {Martin T.} and Wasielewski, {Michael R}",
year = "2018",
month = "1",
day = "1",
doi = "10.1021/jacs.8b08627",
language = "English",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - Two-Dimensional Electronic Spectroscopy Reveals Excitation Energy-Dependent State Mixing during Singlet Fission in a Terrylenediimide Dimer

AU - Mandal, Aritra

AU - Chen, Michelle

AU - Foszcz, Eileen D.

AU - Schultz, Jonathan D.

AU - Kearns, Nicholas M.

AU - Young, Ryan M.

AU - Zanni, Martin T.

AU - Wasielewski, Michael R

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Singlet fission (SF) is a spin-allowed process in which a singlet exciton, 1(S1S0), within an assembly of two or more chromophores spontaneously down-converts into two triplet excitons via a multiexciton correlated triplet pair state, 1(T1T1). To elucidate the involvement of charge transfer (CT) states and vibronic coupling in SF, we performed 2D electronic spectroscopy (2DES) on dilute solutions of a covalently linked, slip-stacked terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer. This dimer undergoes efficient SF in nonpolar 1,4-dioxane and symmetry-breaking charge separation in polar dichloromethane. The various 2DES spectral features in 1,4-dioxane show different pump wavelength dependencies, supporting the presence of mixed states with variable 1(S1S0), 1(T1T1) and CT contributions that evolve with time. Analysis of the 2DES spectra in dichloromethane reveals the presence of a state having largely 1(T1T1) character during charge separation. Therefore, the 1(T1T1) multiexciton state plays an important role in the photophysics of this TDI dimer irrespective of solvent polarity.

AB - Singlet fission (SF) is a spin-allowed process in which a singlet exciton, 1(S1S0), within an assembly of two or more chromophores spontaneously down-converts into two triplet excitons via a multiexciton correlated triplet pair state, 1(T1T1). To elucidate the involvement of charge transfer (CT) states and vibronic coupling in SF, we performed 2D electronic spectroscopy (2DES) on dilute solutions of a covalently linked, slip-stacked terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer. This dimer undergoes efficient SF in nonpolar 1,4-dioxane and symmetry-breaking charge separation in polar dichloromethane. The various 2DES spectral features in 1,4-dioxane show different pump wavelength dependencies, supporting the presence of mixed states with variable 1(S1S0), 1(T1T1) and CT contributions that evolve with time. Analysis of the 2DES spectra in dichloromethane reveals the presence of a state having largely 1(T1T1) character during charge separation. Therefore, the 1(T1T1) multiexciton state plays an important role in the photophysics of this TDI dimer irrespective of solvent polarity.

UR - http://www.scopus.com/inward/record.url?scp=85058860384&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85058860384&partnerID=8YFLogxK

U2 - 10.1021/jacs.8b08627

DO - 10.1021/jacs.8b08627

M3 - Article

C2 - 30501193

AN - SCOPUS:85058860384

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -