Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes

Eric A. Margulies; Yi Lin Wu; Przemyslaw Gawel; Stephen A. Miller; Leah E. Shoer; Richard D. Schaller; François Diederich; Michael R. Wasielewski

doi:10.1002/anie.201501355

Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes

Eric A. Margulies, Yi Lin Wu, Przemyslaw Gawel, Stephen A. Miller, Leah E. Shoer, Richard D. Schaller, François Diederich^*, Michael R. Wasielewski

^*Corresponding author for this work

Chemistry

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59 Scopus citations

Abstract

Thin films of 5,11-dicyano-6,12-diphenyltetracene (TcCN) have been studied for their ability to undergo singlet exciton fission (SF). Functionalization of tetracene with cyano substituents yields a more stable chromophore with favorable energetics for exoergic SF (2E(T₁)-E(S₁)=-0.17 eV), where S₁ and T₁ are singlet and triplet excitons, respectively. As a result of tuning the triplet-state energy, SF is faster in TcCN relative to the corresponding endoergic process in tetracene. SF proceeds with two time constants in the film samples (τ=0.8±0.2 ps and τ=23±3 ps), which is attributed to structural disorder within the film giving rise to one population with a favorable interchromophore geometry, which undergoes rapid SF, and a second population in which the initially formed singlet exciton must diffuse to a site at which this favorable geometry exists. A triplet yield analysis using transient absorption spectra indicates the formation of 1.6±0.3 triplets per initial excited state.

Original language	English (US)
Pages (from-to)	8679-8683
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	30
DOIs	https://doi.org/10.1002/anie.201501355
State	Published - Jul 20 2015

Keywords

chromophores
photophysics
singlet fission
tetracene derivatives
time-resolved spectroscopy

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.201501355

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@article{84a083bd43c54227b3ff36282b3a332f,

title = "Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes",

abstract = "Thin films of 5,11-dicyano-6,12-diphenyltetracene (TcCN) have been studied for their ability to undergo singlet exciton fission (SF). Functionalization of tetracene with cyano substituents yields a more stable chromophore with favorable energetics for exoergic SF (2E(T1)-E(S1)=-0.17 eV), where S1 and T1 are singlet and triplet excitons, respectively. As a result of tuning the triplet-state energy, SF is faster in TcCN relative to the corresponding endoergic process in tetracene. SF proceeds with two time constants in the film samples (τ=0.8±0.2 ps and τ=23±3 ps), which is attributed to structural disorder within the film giving rise to one population with a favorable interchromophore geometry, which undergoes rapid SF, and a second population in which the initially formed singlet exciton must diffuse to a site at which this favorable geometry exists. A triplet yield analysis using transient absorption spectra indicates the formation of 1.6±0.3 triplets per initial excited state.",

keywords = "chromophores, photophysics, singlet fission, tetracene derivatives, time-resolved spectroscopy",

author = "Margulies, {Eric A.} and Wu, {Yi Lin} and Przemyslaw Gawel and Miller, {Stephen A.} and Shoer, {Leah E.} and Schaller, {Richard D.} and Fran{\c c}ois Diederich and Wasielewski, {Michael R.}",

note = "Publisher Copyright: {\textcopyright} 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2015",

month = jul,

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doi = "10.1002/anie.201501355",

language = "English (US)",

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T1 - Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes

AU - Margulies, Eric A.

AU - Wu, Yi Lin

AU - Gawel, Przemyslaw

AU - Miller, Stephen A.

AU - Shoer, Leah E.

AU - Schaller, Richard D.

AU - Diederich, François

AU - Wasielewski, Michael R.

PY - 2015/7/20

Y1 - 2015/7/20

N2 - Thin films of 5,11-dicyano-6,12-diphenyltetracene (TcCN) have been studied for their ability to undergo singlet exciton fission (SF). Functionalization of tetracene with cyano substituents yields a more stable chromophore with favorable energetics for exoergic SF (2E(T1)-E(S1)=-0.17 eV), where S1 and T1 are singlet and triplet excitons, respectively. As a result of tuning the triplet-state energy, SF is faster in TcCN relative to the corresponding endoergic process in tetracene. SF proceeds with two time constants in the film samples (τ=0.8±0.2 ps and τ=23±3 ps), which is attributed to structural disorder within the film giving rise to one population with a favorable interchromophore geometry, which undergoes rapid SF, and a second population in which the initially formed singlet exciton must diffuse to a site at which this favorable geometry exists. A triplet yield analysis using transient absorption spectra indicates the formation of 1.6±0.3 triplets per initial excited state.

AB - Thin films of 5,11-dicyano-6,12-diphenyltetracene (TcCN) have been studied for their ability to undergo singlet exciton fission (SF). Functionalization of tetracene with cyano substituents yields a more stable chromophore with favorable energetics for exoergic SF (2E(T1)-E(S1)=-0.17 eV), where S1 and T1 are singlet and triplet excitons, respectively. As a result of tuning the triplet-state energy, SF is faster in TcCN relative to the corresponding endoergic process in tetracene. SF proceeds with two time constants in the film samples (τ=0.8±0.2 ps and τ=23±3 ps), which is attributed to structural disorder within the film giving rise to one population with a favorable interchromophore geometry, which undergoes rapid SF, and a second population in which the initially formed singlet exciton must diffuse to a site at which this favorable geometry exists. A triplet yield analysis using transient absorption spectra indicates the formation of 1.6±0.3 triplets per initial excited state.

KW - chromophores

KW - photophysics

KW - singlet fission

KW - tetracene derivatives

KW - time-resolved spectroscopy

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Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes

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