Synthesis and photophysical properties of donor- and acceptor-substituted 1,7-bis(arylalkynyl)perylene-3,4: 9,10-bis(dicarboximide)s

Zesheng An, Susan A. Odom, Richard F. Kelley, Chun Huang, Xuan Zhang, Stephen Barlow, Lazaro A. Padilha, Jie Fu, Scott Webster, David J. Hagan, Eric W. Van Stryland, Michael R Wasielewski, Seth R. Marder

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Abstract

A series of 1,7-bis(arylethynyl)-N,N′-bis[2,6-diisopropylphenyl] perylene-3,4:9,10-bis(dicarboximide)s has been obtained from Sonogashira coupling of the 1,7-dibromoperylene-3,4:9,10-bis(dicarboximide) with p-substituted phenylacetylenes in which the p-substituents include π-donors (dialkylamino, diarylamino, p-(diarylami-no)phenyl, alkoxy) and π-acceptors (diarylboryl, p-(diarylboryl)phenyl). The bis(arylethynyl)-substituted chromophores all show two reversible molecular reductions and are all slightly more readily reduced than unsubstituted perylene-3,4:9,10-bis(dicarboximide)s with the electrochemical potentials being rather insensitive to the π-donor or acceptor nature of the aryl group. The amine derivatives also show reversible molecular oxidations. The UV-vis spectra of the chromophores with alkoxy and boryl substituents show red-shifted absorptions relative to unsubstituted perylene diimides with discernible vibronic structure. In contrast, the lowest energy absorptions of the amino derivatives are broad and structureless, suggesting donor-to-acceptor charge-transfer character. Transient absorption spectra for the amine derivatives were interpreted in terms of ultrafast charge separation, followed by charge recombination on a time scale of ca. 80-2000 ps. Two compounds were also synthesized in which an additional stronger, but more weakly coupled, donor group is linked by a nonconjugated bridge to the p-amine donor, to investigate the effect on the charge recombination lifetimes; however, the lifetimes of the charge-separated states, ca. 150 and 1000 ps, were within the range observed for the simple amine systems. Finally, the two-photon absorption properties of three bis(arylethynyl)-substituted derivatives were investigated, along with those of 1,7-di(pyrrolidin-l-y1)-N,N′-bis[2,6- diisopro-pylphenyl]perylene-3,4:9,10-bis(dicarboximide). As with other perylene-3,4:9,10-bis(dicarboximide)s and related species, strong two-photon absorption (>1000 GM) was observed for three of these species close to the one-photon absorption edge; however, an additional feature (100-500 GM) was also observed at longer wavelength. An example with (p-aminophenyl)ethylnyl substituents showed a qualitatively different two-photon spectrum with a cross-section >500 GM being observed over a broad wavelength range.

Original languageEnglish
Pages (from-to)5585-5593
Number of pages9
JournalJournal of Physical Chemistry A
Volume113
Issue number19
DOIs
Publication statusPublished - May 14 2009

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Perylene
amines
Amines
Photons
photons
Derivatives
synthesis
chromophores
Chromophores
life (durability)
energy absorption
polarization (charge separation)
Wavelength
wavelengths
Energy absorption
charge transfer
Charge transfer
Absorption spectra
absorption spectra
oxidation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Synthesis and photophysical properties of donor- and acceptor-substituted 1,7-bis(arylalkynyl)perylene-3,4 : 9,10-bis(dicarboximide)s. / An, Zesheng; Odom, Susan A.; Kelley, Richard F.; Huang, Chun; Zhang, Xuan; Barlow, Stephen; Padilha, Lazaro A.; Fu, Jie; Webster, Scott; Hagan, David J.; Van Stryland, Eric W.; Wasielewski, Michael R; Marder, Seth R.

In: Journal of Physical Chemistry A, Vol. 113, No. 19, 14.05.2009, p. 5585-5593.

Research output: Contribution to journalArticle

An, Z, Odom, SA, Kelley, RF, Huang, C, Zhang, X, Barlow, S, Padilha, LA, Fu, J, Webster, S, Hagan, DJ, Van Stryland, EW, Wasielewski, MR & Marder, SR 2009, 'Synthesis and photophysical properties of donor- and acceptor-substituted 1,7-bis(arylalkynyl)perylene-3,4: 9,10-bis(dicarboximide)s', Journal of Physical Chemistry A, vol. 113, no. 19, pp. 5585-5593. https://doi.org/10.1021/jp900152r
An, Zesheng ; Odom, Susan A. ; Kelley, Richard F. ; Huang, Chun ; Zhang, Xuan ; Barlow, Stephen ; Padilha, Lazaro A. ; Fu, Jie ; Webster, Scott ; Hagan, David J. ; Van Stryland, Eric W. ; Wasielewski, Michael R ; Marder, Seth R. / Synthesis and photophysical properties of donor- and acceptor-substituted 1,7-bis(arylalkynyl)perylene-3,4 : 9,10-bis(dicarboximide)s. In: Journal of Physical Chemistry A. 2009 ; Vol. 113, No. 19. pp. 5585-5593.
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abstract = "A series of 1,7-bis(arylethynyl)-N,N′-bis[2,6-diisopropylphenyl] perylene-3,4:9,10-bis(dicarboximide)s has been obtained from Sonogashira coupling of the 1,7-dibromoperylene-3,4:9,10-bis(dicarboximide) with p-substituted phenylacetylenes in which the p-substituents include π-donors (dialkylamino, diarylamino, p-(diarylami-no)phenyl, alkoxy) and π-acceptors (diarylboryl, p-(diarylboryl)phenyl). The bis(arylethynyl)-substituted chromophores all show two reversible molecular reductions and are all slightly more readily reduced than unsubstituted perylene-3,4:9,10-bis(dicarboximide)s with the electrochemical potentials being rather insensitive to the π-donor or acceptor nature of the aryl group. The amine derivatives also show reversible molecular oxidations. The UV-vis spectra of the chromophores with alkoxy and boryl substituents show red-shifted absorptions relative to unsubstituted perylene diimides with discernible vibronic structure. In contrast, the lowest energy absorptions of the amino derivatives are broad and structureless, suggesting donor-to-acceptor charge-transfer character. Transient absorption spectra for the amine derivatives were interpreted in terms of ultrafast charge separation, followed by charge recombination on a time scale of ca. 80-2000 ps. Two compounds were also synthesized in which an additional stronger, but more weakly coupled, donor group is linked by a nonconjugated bridge to the p-amine donor, to investigate the effect on the charge recombination lifetimes; however, the lifetimes of the charge-separated states, ca. 150 and 1000 ps, were within the range observed for the simple amine systems. Finally, the two-photon absorption properties of three bis(arylethynyl)-substituted derivatives were investigated, along with those of 1,7-di(pyrrolidin-l-y1)-N,N′-bis[2,6- diisopro-pylphenyl]perylene-3,4:9,10-bis(dicarboximide). As with other perylene-3,4:9,10-bis(dicarboximide)s and related species, strong two-photon absorption (>1000 GM) was observed for three of these species close to the one-photon absorption edge; however, an additional feature (100-500 GM) was also observed at longer wavelength. An example with (p-aminophenyl)ethylnyl substituents showed a qualitatively different two-photon spectrum with a cross-section >500 GM being observed over a broad wavelength range.",
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T1 - Synthesis and photophysical properties of donor- and acceptor-substituted 1,7-bis(arylalkynyl)perylene-3,4

T2 - 9,10-bis(dicarboximide)s

AU - An, Zesheng

AU - Odom, Susan A.

AU - Kelley, Richard F.

AU - Huang, Chun

AU - Zhang, Xuan

AU - Barlow, Stephen

AU - Padilha, Lazaro A.

AU - Fu, Jie

AU - Webster, Scott

AU - Hagan, David J.

AU - Van Stryland, Eric W.

AU - Wasielewski, Michael R

AU - Marder, Seth R.

PY - 2009/5/14

Y1 - 2009/5/14

N2 - A series of 1,7-bis(arylethynyl)-N,N′-bis[2,6-diisopropylphenyl] perylene-3,4:9,10-bis(dicarboximide)s has been obtained from Sonogashira coupling of the 1,7-dibromoperylene-3,4:9,10-bis(dicarboximide) with p-substituted phenylacetylenes in which the p-substituents include π-donors (dialkylamino, diarylamino, p-(diarylami-no)phenyl, alkoxy) and π-acceptors (diarylboryl, p-(diarylboryl)phenyl). The bis(arylethynyl)-substituted chromophores all show two reversible molecular reductions and are all slightly more readily reduced than unsubstituted perylene-3,4:9,10-bis(dicarboximide)s with the electrochemical potentials being rather insensitive to the π-donor or acceptor nature of the aryl group. The amine derivatives also show reversible molecular oxidations. The UV-vis spectra of the chromophores with alkoxy and boryl substituents show red-shifted absorptions relative to unsubstituted perylene diimides with discernible vibronic structure. In contrast, the lowest energy absorptions of the amino derivatives are broad and structureless, suggesting donor-to-acceptor charge-transfer character. Transient absorption spectra for the amine derivatives were interpreted in terms of ultrafast charge separation, followed by charge recombination on a time scale of ca. 80-2000 ps. Two compounds were also synthesized in which an additional stronger, but more weakly coupled, donor group is linked by a nonconjugated bridge to the p-amine donor, to investigate the effect on the charge recombination lifetimes; however, the lifetimes of the charge-separated states, ca. 150 and 1000 ps, were within the range observed for the simple amine systems. Finally, the two-photon absorption properties of three bis(arylethynyl)-substituted derivatives were investigated, along with those of 1,7-di(pyrrolidin-l-y1)-N,N′-bis[2,6- diisopro-pylphenyl]perylene-3,4:9,10-bis(dicarboximide). As with other perylene-3,4:9,10-bis(dicarboximide)s and related species, strong two-photon absorption (>1000 GM) was observed for three of these species close to the one-photon absorption edge; however, an additional feature (100-500 GM) was also observed at longer wavelength. An example with (p-aminophenyl)ethylnyl substituents showed a qualitatively different two-photon spectrum with a cross-section >500 GM being observed over a broad wavelength range.

AB - A series of 1,7-bis(arylethynyl)-N,N′-bis[2,6-diisopropylphenyl] perylene-3,4:9,10-bis(dicarboximide)s has been obtained from Sonogashira coupling of the 1,7-dibromoperylene-3,4:9,10-bis(dicarboximide) with p-substituted phenylacetylenes in which the p-substituents include π-donors (dialkylamino, diarylamino, p-(diarylami-no)phenyl, alkoxy) and π-acceptors (diarylboryl, p-(diarylboryl)phenyl). The bis(arylethynyl)-substituted chromophores all show two reversible molecular reductions and are all slightly more readily reduced than unsubstituted perylene-3,4:9,10-bis(dicarboximide)s with the electrochemical potentials being rather insensitive to the π-donor or acceptor nature of the aryl group. The amine derivatives also show reversible molecular oxidations. The UV-vis spectra of the chromophores with alkoxy and boryl substituents show red-shifted absorptions relative to unsubstituted perylene diimides with discernible vibronic structure. In contrast, the lowest energy absorptions of the amino derivatives are broad and structureless, suggesting donor-to-acceptor charge-transfer character. Transient absorption spectra for the amine derivatives were interpreted in terms of ultrafast charge separation, followed by charge recombination on a time scale of ca. 80-2000 ps. Two compounds were also synthesized in which an additional stronger, but more weakly coupled, donor group is linked by a nonconjugated bridge to the p-amine donor, to investigate the effect on the charge recombination lifetimes; however, the lifetimes of the charge-separated states, ca. 150 and 1000 ps, were within the range observed for the simple amine systems. Finally, the two-photon absorption properties of three bis(arylethynyl)-substituted derivatives were investigated, along with those of 1,7-di(pyrrolidin-l-y1)-N,N′-bis[2,6- diisopro-pylphenyl]perylene-3,4:9,10-bis(dicarboximide). As with other perylene-3,4:9,10-bis(dicarboximide)s and related species, strong two-photon absorption (>1000 GM) was observed for three of these species close to the one-photon absorption edge; however, an additional feature (100-500 GM) was also observed at longer wavelength. An example with (p-aminophenyl)ethylnyl substituents showed a qualitatively different two-photon spectrum with a cross-section >500 GM being observed over a broad wavelength range.

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