Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes

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 an...

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Published inAngewandte Chemie (International ed.) Vol. 54; no. 30; pp. 8679 - 8683
Main Authors Margulies, Eric A., Wu, Yi-Lin, Gawel, Przemyslaw, Miller, Stephen A., Shoer, Leah E., Schaller, Richard D., Diederich, François, Wasielewski, Michael R.
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 20.07.2015
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
chromophores
Diffusion
Disorders
Excitation
Excitation spectra
Fission
Formations
photophysics
singlet fission
tetracene derivatives
Thin films
time-resolved spectroscopy
Tuning
time-resolved spectroscopy
chromophores
photophysics
tetracene derivatives
singlet fission
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Summary: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. Divide and conquer: Transient absorption measurements reveal sub‐picosecond singlet exciton fission in thin films of a cyano‐substituted diaryltetracene. A triplet yield analysis of the transient absorption data set indicates the formation of 1.6±0.3 triplet excitons per singlet exciton, as a result of rapid and efficient singlet fission.
Bibliography:Swiss National Science Foundation
Office of Basic Energy Sciences, U.S. Department of Energy (DOE) - No. DE-FG02-99ER14999
National Science Foundation - No. DMR-1121262
This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, U.S. Department of Energy (DOE), under Grant No. DE-FG02-99ER14999 (M.R.W.), the Swiss National Science Foundation, and the ERC Advanced Grant No. 246637 ("OPTELOMAC"). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences User Facility under Contract No. DE-AC02-06CH11357. This work made use of the J. B. Cohen X-ray Diffraction Facility at the Materials Research Center of Northwestern University supported by the National Science Foundation MRSEC program (DMR-1121262). We thank Dr. Matthew Krzyaniak and Dr. Samuel Eaton for help with data analysis, acquiring time-resolved fluorescence data, and helpful discussions.
ArticleID:ANIE201501355
ERC - No. 246637
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This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, U.S. Department of Energy (DOE), under Grant No. DE‐FG02‐99ER14999 (M.R.W.), the Swiss National Science Foundation, and the ERC Advanced Grant No. 246637 (“OPTELOMAC”). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences User Facility under Contract No. DE‐AC02‐06CH11357. This work made use of the J. B. Cohen X‐ray Diffraction Facility at the Materials Research Center of Northwestern University supported by the National Science Foundation MRSEC program (DMR‐1121262). We thank Dr. Matthew Krzyaniak and Dr. Samuel Eaton for help with data analysis, acquiring time‐resolved fluorescence data, and helpful discussions.
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SourceType-Scholarly Journals-1
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201501355