Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles

Yilei Wu; Ryan M. Young; Marco Frasconi; Severin T. Schneebeli; Peter Spenst; Daniel M. Gardner; Kristen E. Brown; Frank Würthner; J. Fraser Stoddart; Michael R. Wasielewski

doi:10.1021/jacs.5b08386

Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles

Yilei Wu, Ryan M. Young, Marco Frasconi, Severin T. Schneebeli, Peter Spenst, Daniel M. Gardner, Kristen E. Brown, Frank Würthner^*, J. Fraser Stoddart, Michael R. Wasielewski

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

100 Scopus citations

Abstract

We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH₂Cl₂ gives PDI^+•-PDI^-• in Δ_CS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI^+•-PDI^-• to the ground state occurs in Δ_CR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

Original language	English (US)
Pages (from-to)	13236-13239
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	41
DOIs	https://doi.org/10.1021/jacs.5b08386
State	Published - Oct 21 2015

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Wu, Y., Young, R. M., Frasconi, M., Schneebeli, S. T., Spenst, P., Gardner, D. M., Brown, K. E., Würthner, F., Stoddart, J. F., & Wasielewski, M. R. (2015). Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles. Journal of the American Chemical Society, 137(41), 13236-13239. https://doi.org/10.1021/jacs.5b08386

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abstract = "We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI+•-PDI-• in ΔCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI+•-PDI-• to the ground state occurs in ΔCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.",

author = "Yilei Wu and Young, {Ryan M.} and Marco Frasconi and Schneebeli, {Severin T.} and Peter Spenst and Gardner, {Daniel M.} and Brown, {Kristen E.} and Frank W{\"u}rthner and Stoddart, {J. Fraser} and Wasielewski, {Michael R.}",

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AU - Spenst, Peter

AU - Gardner, Daniel M.

AU - Brown, Kristen E.

AU - Würthner, Frank

AU - Stoddart, J. Fraser

AU - Wasielewski, Michael R.

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N2 - We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI+•-PDI-• in ΔCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI+•-PDI-• to the ground state occurs in ΔCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

AB - We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI+•-PDI-• in ΔCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI+•-PDI-• to the ground state occurs in ΔCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

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Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles

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