Singlet exciton fission in thin films of tert -butyl-substituted terrylenes

Samuel W. Eaton, Stephen A. Miller, Eric A. Margulies, Leah E. Shoer, Richard D Schaller, Michael R Wasielewski

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (τ = 120 ± 10 ps) and 2 (τ = 320 ± 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 ± 20% for 1 and 200 ± 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.

Original languageEnglish
Pages (from-to)4151-4161
Number of pages11
JournalJournal of Physical Chemistry A
Volume119
Issue number18
DOIs
Publication statusPublished - May 7 2015

Fingerprint

fission
excitons
Thin films
Chromophores
thin films
chromophores
Vapors
vapors
Phosphorescence
crystal morphology
LDS 751
excimers
phosphorescence
Dimers
crystallinity
fluence
slip
Fluorescence
dimers
Crystalline materials

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Singlet exciton fission in thin films of tert -butyl-substituted terrylenes. / Eaton, Samuel W.; Miller, Stephen A.; Margulies, Eric A.; Shoer, Leah E.; Schaller, Richard D; Wasielewski, Michael R.

In: Journal of Physical Chemistry A, Vol. 119, No. 18, 07.05.2015, p. 4151-4161.

Research output: Contribution to journalArticle

Eaton, Samuel W. ; Miller, Stephen A. ; Margulies, Eric A. ; Shoer, Leah E. ; Schaller, Richard D ; Wasielewski, Michael R. / Singlet exciton fission in thin films of tert -butyl-substituted terrylenes. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 18. pp. 4151-4161.
@article{66a51ca59f684445aa38b2ecaa81d304,
title = "Singlet exciton fission in thin films of tert -butyl-substituted terrylenes",
abstract = "Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (τ = 120 ± 10 ps) and 2 (τ = 320 ± 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 ± 20{\%} for 1 and 200 ± 30{\%} for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.",
author = "Eaton, {Samuel W.} and Miller, {Stephen A.} and Margulies, {Eric A.} and Shoer, {Leah E.} and Schaller, {Richard D} and Wasielewski, {Michael R}",
year = "2015",
month = "5",
day = "7",
doi = "10.1021/acs.jpca.5b02719",
language = "English",
volume = "119",
pages = "4151--4161",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "18",

}

TY - JOUR

T1 - Singlet exciton fission in thin films of tert -butyl-substituted terrylenes

AU - Eaton, Samuel W.

AU - Miller, Stephen A.

AU - Margulies, Eric A.

AU - Shoer, Leah E.

AU - Schaller, Richard D

AU - Wasielewski, Michael R

PY - 2015/5/7

Y1 - 2015/5/7

N2 - Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (τ = 120 ± 10 ps) and 2 (τ = 320 ± 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 ± 20% for 1 and 200 ± 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.

AB - Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (τ = 120 ± 10 ps) and 2 (τ = 320 ± 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 ± 20% for 1 and 200 ± 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.

UR - http://www.scopus.com/inward/record.url?scp=84929011850&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84929011850&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.5b02719

DO - 10.1021/acs.jpca.5b02719

M3 - Article

AN - SCOPUS:84929011850

VL - 119

SP - 4151

EP - 4161

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 18

ER -