Direct observation of a charge-transfer state preceding high-yield singlet fission in terrylenediimide thin films

Eric A. Margulies; Jenna L. Logsdon; Claire E. Miller; Lin Ma; Ethan Simonoff; Ryan M. Young; George C. Schatz; Michael R. Wasielewski

doi:10.1021/jacs.6b07721

Direct observation of a charge-transfer state preceding high-yield singlet fission in terrylenediimide thin films

Eric A. Margulies, Jenna L. Logsdon, Claire E. Miller, Lin Ma, Ethan Simonoff, Ryan M. Young, George C. Schatz, Michael R. Wasielewski^*

^*Corresponding author for this work

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

161 Scopus citations

Abstract

Singlet exciton fission (SF) in organic chromophore assemblies results in the conversion of one singlet exciton (S₁) into two triplet excitons (T₁), provided that the overall process is exoergic, i.e., E(S₁) > 2E(T₁). We report on SF in thin polycrystalline films of two terrylene-3, 4:ll, 12-bis(dicarboximide) (TDI) derivatives 1 and 2, which crystallize into two distinct π-stacked structures. Femtosecond transient absorption spectroscopy (fsTA) reveals a charge-transfer state preceding a 190% T, yield in films of 1, where the π-stacked TDI molecules are rotated by 23° along an axis perpendicular to their n systems. In contrast, when the TDI molecules are slip-stacked along their N-N axes in films of 2, fsTA shows excimer formation, followed by a 50% T₁ yield.

Original language	English (US)
Pages (from-to)	663-671
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	139
Issue number	2
DOIs	https://doi.org/10.1021/jacs.6b07721
State	Published - Jan 18 2017

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.6b07721

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title = "Direct observation of a charge-transfer state preceding high-yield singlet fission in terrylenediimide thin films",

abstract = "Singlet exciton fission (SF) in organic chromophore assemblies results in the conversion of one singlet exciton (S1) into two triplet excitons (T1), provided that the overall process is exoergic, i.e., E(S1) > 2E(T1). We report on SF in thin polycrystalline films of two terrylene-3, 4:ll, 12-bis(dicarboximide) (TDI) derivatives 1 and 2, which crystallize into two distinct π-stacked structures. Femtosecond transient absorption spectroscopy (fsTA) reveals a charge-transfer state preceding a 190% T, yield in films of 1, where the π-stacked TDI molecules are rotated by 23° along an axis perpendicular to their n systems. In contrast, when the TDI molecules are slip-stacked along their N-N axes in films of 2, fsTA shows excimer formation, followed by a 50% T1 yield.",

author = "Margulies, {Eric A.} and Logsdon, {Jenna L.} and Miller, {Claire E.} and Lin Ma and Ethan Simonoff and Young, {Ryan M.} and Schatz, {George C.} and Wasielewski, {Michael R.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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doi = "10.1021/jacs.6b07721",

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T1 - Direct observation of a charge-transfer state preceding high-yield singlet fission in terrylenediimide thin films

AU - Margulies, Eric A.

AU - Logsdon, Jenna L.

AU - Miller, Claire E.

AU - Ma, Lin

AU - Simonoff, Ethan

AU - Young, Ryan M.

AU - Schatz, George C.

AU - Wasielewski, Michael R.

PY - 2017/1/18

Y1 - 2017/1/18

N2 - Singlet exciton fission (SF) in organic chromophore assemblies results in the conversion of one singlet exciton (S1) into two triplet excitons (T1), provided that the overall process is exoergic, i.e., E(S1) > 2E(T1). We report on SF in thin polycrystalline films of two terrylene-3, 4:ll, 12-bis(dicarboximide) (TDI) derivatives 1 and 2, which crystallize into two distinct π-stacked structures. Femtosecond transient absorption spectroscopy (fsTA) reveals a charge-transfer state preceding a 190% T, yield in films of 1, where the π-stacked TDI molecules are rotated by 23° along an axis perpendicular to their n systems. In contrast, when the TDI molecules are slip-stacked along their N-N axes in films of 2, fsTA shows excimer formation, followed by a 50% T1 yield.

AB - Singlet exciton fission (SF) in organic chromophore assemblies results in the conversion of one singlet exciton (S1) into two triplet excitons (T1), provided that the overall process is exoergic, i.e., E(S1) > 2E(T1). We report on SF in thin polycrystalline films of two terrylene-3, 4:ll, 12-bis(dicarboximide) (TDI) derivatives 1 and 2, which crystallize into two distinct π-stacked structures. Femtosecond transient absorption spectroscopy (fsTA) reveals a charge-transfer state preceding a 190% T, yield in films of 1, where the π-stacked TDI molecules are rotated by 23° along an axis perpendicular to their n systems. In contrast, when the TDI molecules are slip-stacked along their N-N axes in films of 2, fsTA shows excimer formation, followed by a 50% T1 yield.

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JF - Journal of the American Chemical Society

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Direct observation of a charge-transfer state preceding high-yield singlet fission in terrylenediimide thin films

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CCDC 1491229: Experimental Crystal Structure Determination

CCDC 1491228: Experimental Crystal Structure Determination

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Direct observation of a charge-transfer state preceding high-yield singlet fission in terrylenediimide thin films

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CCDC 1491229: Experimental Crystal Structure Determination

CCDC 1491228: Experimental Crystal Structure Determination

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