Energy flow dynamics within cofacial and slip-stacked perylene-3,4-dicarboximide dimer models of π-aggregates

Rebecca J. Lindquist, Kelly M. Lefler, Kristen E. Brown, Scott M. Dyar, Eric A. Margulies, Ryan M. Young, Michael R Wasielewski

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

Robust perylene-3,4-dicarboximide (PMI) π-aggregates provide important light-harvesting and electron-hole pair generation advantages in organic photovoltaics and related applications, but relatively few studies have focused on the electronic interactions between PMI chromophores. In contrast, structure-function relationships based on π-π stacking in the related perylene-3,4:9,10-bis(dicarboximides) (PDIs) have been widely investigated. The performance of both PMI and PDI derivatives in organic devices may be limited by the formation of low-energy excimer trap states in morphologies where interchromophore coupling is strong. Here, five covalently bound PMI dimers with varying degrees of electronic interaction were studied to probe the relative chromophore orientations that lead to excimer energy trap states. Femtosecond near-infrared transient absorption spectroscopy was used to observe the growth of a low-energy transition at ∼1450-1520 nm characteristic of the excimer state in these covalent dimers. The excimer-state absorption appears in ∼1 ps, followed by conformational relaxation over 8-17 ps. The excimer state then decays in 6.9-12.8 ns, as measured by time-resolved fluorescence spectroscopy. The excimer lifetimes reach a maximum for a slip-stacked geometry in which the two PMI molecules are displaced along their long axes by one phenyl group (∼4.3 A˚). Additional displacement of the PMIs by a biphenyl spacer along the long axis prevents excimer formation. Symmetry-breaking charge transfer is not observed in any of the PMI dimers, and only a small triplet yield (

Original languageEnglish
Pages (from-to)14912-14923
Number of pages12
JournalJournal of the American Chemical Society
Volume136
Issue number42
DOIs
Publication statusPublished - Oct 22 2014

Fingerprint

Perylene
Dimers
Chromophores
Fluorescence Spectrometry
Spectrum Analysis
Fluorescence spectroscopy
Electrons
Absorption spectroscopy
Light
Equipment and Supplies
Charge transfer
Growth
Infrared radiation
Derivatives
Molecules
Geometry

ASJC Scopus subject areas

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

Cite this

Energy flow dynamics within cofacial and slip-stacked perylene-3,4-dicarboximide dimer models of π-aggregates. / Lindquist, Rebecca J.; Lefler, Kelly M.; Brown, Kristen E.; Dyar, Scott M.; Margulies, Eric A.; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 136, No. 42, 22.10.2014, p. 14912-14923.

Research output: Contribution to journalArticle

Lindquist, Rebecca J. ; Lefler, Kelly M. ; Brown, Kristen E. ; Dyar, Scott M. ; Margulies, Eric A. ; Young, Ryan M. ; Wasielewski, Michael R. / Energy flow dynamics within cofacial and slip-stacked perylene-3,4-dicarboximide dimer models of π-aggregates. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 42. pp. 14912-14923.
@article{6ca017c153d34932a68d79f573f52653,
title = "Energy flow dynamics within cofacial and slip-stacked perylene-3,4-dicarboximide dimer models of π-aggregates",
abstract = "Robust perylene-3,4-dicarboximide (PMI) π-aggregates provide important light-harvesting and electron-hole pair generation advantages in organic photovoltaics and related applications, but relatively few studies have focused on the electronic interactions between PMI chromophores. In contrast, structure-function relationships based on π-π stacking in the related perylene-3,4:9,10-bis(dicarboximides) (PDIs) have been widely investigated. The performance of both PMI and PDI derivatives in organic devices may be limited by the formation of low-energy excimer trap states in morphologies where interchromophore coupling is strong. Here, five covalently bound PMI dimers with varying degrees of electronic interaction were studied to probe the relative chromophore orientations that lead to excimer energy trap states. Femtosecond near-infrared transient absorption spectroscopy was used to observe the growth of a low-energy transition at ∼1450-1520 nm characteristic of the excimer state in these covalent dimers. The excimer-state absorption appears in ∼1 ps, followed by conformational relaxation over 8-17 ps. The excimer state then decays in 6.9-12.8 ns, as measured by time-resolved fluorescence spectroscopy. The excimer lifetimes reach a maximum for a slip-stacked geometry in which the two PMI molecules are displaced along their long axes by one phenyl group (∼4.3 A˚). Additional displacement of the PMIs by a biphenyl spacer along the long axis prevents excimer formation. Symmetry-breaking charge transfer is not observed in any of the PMI dimers, and only a small triplet yield (",
author = "Lindquist, {Rebecca J.} and Lefler, {Kelly M.} and Brown, {Kristen E.} and Dyar, {Scott M.} and Margulies, {Eric A.} and Young, {Ryan M.} and Wasielewski, {Michael R}",
year = "2014",
month = "10",
day = "22",
doi = "10.1021/ja507653p",
language = "English",
volume = "136",
pages = "14912--14923",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "42",

}

TY - JOUR

T1 - Energy flow dynamics within cofacial and slip-stacked perylene-3,4-dicarboximide dimer models of π-aggregates

AU - Lindquist, Rebecca J.

AU - Lefler, Kelly M.

AU - Brown, Kristen E.

AU - Dyar, Scott M.

AU - Margulies, Eric A.

AU - Young, Ryan M.

AU - Wasielewski, Michael R

PY - 2014/10/22

Y1 - 2014/10/22

N2 - Robust perylene-3,4-dicarboximide (PMI) π-aggregates provide important light-harvesting and electron-hole pair generation advantages in organic photovoltaics and related applications, but relatively few studies have focused on the electronic interactions between PMI chromophores. In contrast, structure-function relationships based on π-π stacking in the related perylene-3,4:9,10-bis(dicarboximides) (PDIs) have been widely investigated. The performance of both PMI and PDI derivatives in organic devices may be limited by the formation of low-energy excimer trap states in morphologies where interchromophore coupling is strong. Here, five covalently bound PMI dimers with varying degrees of electronic interaction were studied to probe the relative chromophore orientations that lead to excimer energy trap states. Femtosecond near-infrared transient absorption spectroscopy was used to observe the growth of a low-energy transition at ∼1450-1520 nm characteristic of the excimer state in these covalent dimers. The excimer-state absorption appears in ∼1 ps, followed by conformational relaxation over 8-17 ps. The excimer state then decays in 6.9-12.8 ns, as measured by time-resolved fluorescence spectroscopy. The excimer lifetimes reach a maximum for a slip-stacked geometry in which the two PMI molecules are displaced along their long axes by one phenyl group (∼4.3 A˚). Additional displacement of the PMIs by a biphenyl spacer along the long axis prevents excimer formation. Symmetry-breaking charge transfer is not observed in any of the PMI dimers, and only a small triplet yield (

AB - Robust perylene-3,4-dicarboximide (PMI) π-aggregates provide important light-harvesting and electron-hole pair generation advantages in organic photovoltaics and related applications, but relatively few studies have focused on the electronic interactions between PMI chromophores. In contrast, structure-function relationships based on π-π stacking in the related perylene-3,4:9,10-bis(dicarboximides) (PDIs) have been widely investigated. The performance of both PMI and PDI derivatives in organic devices may be limited by the formation of low-energy excimer trap states in morphologies where interchromophore coupling is strong. Here, five covalently bound PMI dimers with varying degrees of electronic interaction were studied to probe the relative chromophore orientations that lead to excimer energy trap states. Femtosecond near-infrared transient absorption spectroscopy was used to observe the growth of a low-energy transition at ∼1450-1520 nm characteristic of the excimer state in these covalent dimers. The excimer-state absorption appears in ∼1 ps, followed by conformational relaxation over 8-17 ps. The excimer state then decays in 6.9-12.8 ns, as measured by time-resolved fluorescence spectroscopy. The excimer lifetimes reach a maximum for a slip-stacked geometry in which the two PMI molecules are displaced along their long axes by one phenyl group (∼4.3 A˚). Additional displacement of the PMIs by a biphenyl spacer along the long axis prevents excimer formation. Symmetry-breaking charge transfer is not observed in any of the PMI dimers, and only a small triplet yield (

UR - http://www.scopus.com/inward/record.url?scp=84908538429&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84908538429&partnerID=8YFLogxK

U2 - 10.1021/ja507653p

DO - 10.1021/ja507653p

M3 - Article

AN - SCOPUS:84908538429

VL - 136

SP - 14912

EP - 14923

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 42

ER -