Excited-state symmetry breaking in cofacial and linear dimers of a green perylenediimide chlorophyll analogue leading to ultrafast charge separation

Jovan M. Giaimo, Alexey V. Gusev, Michael R Wasielewski

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174 Citations (Scopus)

Abstract

Photoexcitation of chromophoric dimers constrained to a symmetric π-stacked geometry by their molecular structure usually produces excimers independent of solvent polarity, while dimers with edge-to-edge perpendicular π systems undergo excited-state symmetry breaking in highly polar solvents leading to intradimer charge separation. We present direct evidence for symmetry breaking in the lowest excited singlet state of a symmetric cofacial dimer of 1,7-bis(pyrrolidin-1′-yl)-perylene-3,4:9,10-bis(dicarboximide) (5PDI) in the low polarity solvent toluene to produce a radical ion pair quantitatively. This dimer, cof-5PDI2, was synthesized by attaching two 5PDI chromophores via imide groups to a xanthene spacer. For comparison, a linear symmetric dimer, lin-5PDI2, was prepared in which the 5PDI chromophores are linked end-to-end via a N-N single bond between their imides. The edge-to-edge π systems of the 5PDI chromophores within lin-5PDI2 are perpendicular to one another. Ground-state absorption spectra of both 5PDI dimers show exciton coupling, which is consistent with the orientation of the 5PDI chromophores relative to one another. Ultrafast transient absorption spectroscopy following excitation of the dimers with 700 nm, 100 fs laser pulses shows that quantitative intradimer electron transfer occurs in cof-5PDI2 in toluene with τ = 0.17 ps followed by charge recombination to the ground state with τ = 222 ps. Similar measurements on lin-5PDI2 reveal that photoinduced electron transfer does not occur in toluene, but occurs in more polar solvents such as 2-methyltetrahydrofuran, wherein τ = 55 ps for charge separation and τ = 99 ps for charge recombination. Excited-state symmetry breaking in 5PDI dimers provides new routes to biomimetic charge separation and storage assemblies that can be more easily prepared and modified than those based on multiple tetrapyrrole macrocycles.

Original languageEnglish
Pages (from-to)8530-8531
Number of pages2
JournalJournal of the American Chemical Society
Volume124
Issue number29
DOIs
Publication statusPublished - Jul 24 2002

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Crystal symmetry
Chlorophyll
Excited states
Dimers
Toluene
Imides
Chromophores
Genetic Recombination
Xanthenes
Tetrapyrroles
Electrons
Biomimetics
Molecular Structure
Ground state
Spectrum Analysis
Lasers
Ions
perylenediimide
Photoexcitation
Absorption spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Excited-state symmetry breaking in cofacial and linear dimers of a green perylenediimide chlorophyll analogue leading to ultrafast charge separation",
abstract = "Photoexcitation of chromophoric dimers constrained to a symmetric π-stacked geometry by their molecular structure usually produces excimers independent of solvent polarity, while dimers with edge-to-edge perpendicular π systems undergo excited-state symmetry breaking in highly polar solvents leading to intradimer charge separation. We present direct evidence for symmetry breaking in the lowest excited singlet state of a symmetric cofacial dimer of 1,7-bis(pyrrolidin-1′-yl)-perylene-3,4:9,10-bis(dicarboximide) (5PDI) in the low polarity solvent toluene to produce a radical ion pair quantitatively. This dimer, cof-5PDI2, was synthesized by attaching two 5PDI chromophores via imide groups to a xanthene spacer. For comparison, a linear symmetric dimer, lin-5PDI2, was prepared in which the 5PDI chromophores are linked end-to-end via a N-N single bond between their imides. The edge-to-edge π systems of the 5PDI chromophores within lin-5PDI2 are perpendicular to one another. Ground-state absorption spectra of both 5PDI dimers show exciton coupling, which is consistent with the orientation of the 5PDI chromophores relative to one another. Ultrafast transient absorption spectroscopy following excitation of the dimers with 700 nm, 100 fs laser pulses shows that quantitative intradimer electron transfer occurs in cof-5PDI2 in toluene with τ = 0.17 ps followed by charge recombination to the ground state with τ = 222 ps. Similar measurements on lin-5PDI2 reveal that photoinduced electron transfer does not occur in toluene, but occurs in more polar solvents such as 2-methyltetrahydrofuran, wherein τ = 55 ps for charge separation and τ = 99 ps for charge recombination. Excited-state symmetry breaking in 5PDI dimers provides new routes to biomimetic charge separation and storage assemblies that can be more easily prepared and modified than those based on multiple tetrapyrrole macrocycles.",
author = "Giaimo, {Jovan M.} and Gusev, {Alexey V.} and Wasielewski, {Michael R}",
year = "2002",
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T1 - Excited-state symmetry breaking in cofacial and linear dimers of a green perylenediimide chlorophyll analogue leading to ultrafast charge separation

AU - Giaimo, Jovan M.

AU - Gusev, Alexey V.

AU - Wasielewski, Michael R

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N2 - Photoexcitation of chromophoric dimers constrained to a symmetric π-stacked geometry by their molecular structure usually produces excimers independent of solvent polarity, while dimers with edge-to-edge perpendicular π systems undergo excited-state symmetry breaking in highly polar solvents leading to intradimer charge separation. We present direct evidence for symmetry breaking in the lowest excited singlet state of a symmetric cofacial dimer of 1,7-bis(pyrrolidin-1′-yl)-perylene-3,4:9,10-bis(dicarboximide) (5PDI) in the low polarity solvent toluene to produce a radical ion pair quantitatively. This dimer, cof-5PDI2, was synthesized by attaching two 5PDI chromophores via imide groups to a xanthene spacer. For comparison, a linear symmetric dimer, lin-5PDI2, was prepared in which the 5PDI chromophores are linked end-to-end via a N-N single bond between their imides. The edge-to-edge π systems of the 5PDI chromophores within lin-5PDI2 are perpendicular to one another. Ground-state absorption spectra of both 5PDI dimers show exciton coupling, which is consistent with the orientation of the 5PDI chromophores relative to one another. Ultrafast transient absorption spectroscopy following excitation of the dimers with 700 nm, 100 fs laser pulses shows that quantitative intradimer electron transfer occurs in cof-5PDI2 in toluene with τ = 0.17 ps followed by charge recombination to the ground state with τ = 222 ps. Similar measurements on lin-5PDI2 reveal that photoinduced electron transfer does not occur in toluene, but occurs in more polar solvents such as 2-methyltetrahydrofuran, wherein τ = 55 ps for charge separation and τ = 99 ps for charge recombination. Excited-state symmetry breaking in 5PDI dimers provides new routes to biomimetic charge separation and storage assemblies that can be more easily prepared and modified than those based on multiple tetrapyrrole macrocycles.

AB - Photoexcitation of chromophoric dimers constrained to a symmetric π-stacked geometry by their molecular structure usually produces excimers independent of solvent polarity, while dimers with edge-to-edge perpendicular π systems undergo excited-state symmetry breaking in highly polar solvents leading to intradimer charge separation. We present direct evidence for symmetry breaking in the lowest excited singlet state of a symmetric cofacial dimer of 1,7-bis(pyrrolidin-1′-yl)-perylene-3,4:9,10-bis(dicarboximide) (5PDI) in the low polarity solvent toluene to produce a radical ion pair quantitatively. This dimer, cof-5PDI2, was synthesized by attaching two 5PDI chromophores via imide groups to a xanthene spacer. For comparison, a linear symmetric dimer, lin-5PDI2, was prepared in which the 5PDI chromophores are linked end-to-end via a N-N single bond between their imides. The edge-to-edge π systems of the 5PDI chromophores within lin-5PDI2 are perpendicular to one another. Ground-state absorption spectra of both 5PDI dimers show exciton coupling, which is consistent with the orientation of the 5PDI chromophores relative to one another. Ultrafast transient absorption spectroscopy following excitation of the dimers with 700 nm, 100 fs laser pulses shows that quantitative intradimer electron transfer occurs in cof-5PDI2 in toluene with τ = 0.17 ps followed by charge recombination to the ground state with τ = 222 ps. Similar measurements on lin-5PDI2 reveal that photoinduced electron transfer does not occur in toluene, but occurs in more polar solvents such as 2-methyltetrahydrofuran, wherein τ = 55 ps for charge separation and τ = 99 ps for charge recombination. Excited-state symmetry breaking in 5PDI dimers provides new routes to biomimetic charge separation and storage assemblies that can be more easily prepared and modified than those based on multiple tetrapyrrole macrocycles.

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