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Two-photon absorption properties of proquinoidal D-A-D and A-D-A quadrupolar chromophores.

Publication ,  Journal Article
Susumu, K; Fisher, JAN; Zheng, J; Beratan, DN; Yodh, AG; Therien, MJ
Published in: The journal of physical chemistry. A
June 2011

We report the synthesis, one- and two-photon absorption spectroscopy, fluorescence, and electrochemical properties of a series of quadrupolar molecules that feature proquinoidal π-aromatic acceptors. These quadrupolar molecules possess either donor-acceptor-donor (D-A-D) or acceptor-donor-acceptor (A-D-A) electronic motifs, and feature 4-N,N-dihexylaminophenyl, 4-dodecyloxyphenyl, 4-(N,N-dihexylamino)benzo[c][1,2,5]thiadiazolyl or 2,5-dioctyloxyphenyl electron donor moieties and benzo[c][1,2,5]thiadiazole (BTD) or 6,7-bis(3',7'-dimethyloctyl)[1,2,5]thiadiazolo[3,4-g]quinoxaline (TDQ) electron acceptor units. These conjugated structures are highly emissive in nonpolar solvents and exhibit large spectral red-shifts of their respective lowest energy absorption bands relative to analogous reference compounds that incorporate phenylene components in place of BTD and TDQ moieties. BTD-based D-A-D and A-D-A chromophores exhibit increasing fluorescence emission red-shifts, and a concomitant decrease of the fluorescence quantum yield (Φ(f)) with increasing solvent polarity; these data indicate that electronic excitation augments benzothiadiazole electron density via an internal charge transfer mechanism. The BTD- and TDQ-containing structures exhibit blue-shifted two-photon absorption (TPA) spectra relative to their corresponding one-photon absorption (OPA) spectra, and display high TPA cross sections (>100 GM) within these spectral windows. D-A-D and A-D-A structures that feature more extensive conjugation within this series of compounds exhibit larger TPA cross sections consistent with computational simulation. Factors governing TPA properties of these quadrupolar chromophores are discussed within the context of a three-state model.

Duke Scholars

Published In

The journal of physical chemistry. A

DOI

EISSN

1520-5215

ISSN

1089-5639

Publication Date

June 2011

Volume

115

Issue

22

Start / End Page

5525 / 5539

Related Subject Headings

  • Thiadiazoles
  • Spectrophotometry, Ultraviolet
  • Quinoxalines
  • Quantum Theory
  • Photons
  • Molecular Structure
  • Fluorescence
  • Electrochemistry
  • 5102 Atomic, molecular and optical physics
  • 3407 Theoretical and computational chemistry
 

Citation

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Susumu, K., Fisher, J. A. N., Zheng, J., Beratan, D. N., Yodh, A. G., & Therien, M. J. (2011). Two-photon absorption properties of proquinoidal D-A-D and A-D-A quadrupolar chromophores. The Journal of Physical Chemistry. A, 115(22), 5525–5539. https://doi.org/10.1021/jp2000738
Susumu, Kimihiro, Jonathan A. N. Fisher, Jieru Zheng, David N. Beratan, Arjun G. Yodh, and Michael J. Therien. “Two-photon absorption properties of proquinoidal D-A-D and A-D-A quadrupolar chromophores.The Journal of Physical Chemistry. A 115, no. 22 (June 2011): 5525–39. https://doi.org/10.1021/jp2000738.
Susumu K, Fisher JAN, Zheng J, Beratan DN, Yodh AG, Therien MJ. Two-photon absorption properties of proquinoidal D-A-D and A-D-A quadrupolar chromophores. The journal of physical chemistry A. 2011 Jun;115(22):5525–39.
Susumu, Kimihiro, et al. “Two-photon absorption properties of proquinoidal D-A-D and A-D-A quadrupolar chromophores.The Journal of Physical Chemistry. A, vol. 115, no. 22, June 2011, pp. 5525–39. Epmc, doi:10.1021/jp2000738.
Susumu K, Fisher JAN, Zheng J, Beratan DN, Yodh AG, Therien MJ. Two-photon absorption properties of proquinoidal D-A-D and A-D-A quadrupolar chromophores. The journal of physical chemistry A. 2011 Jun;115(22):5525–5539.
Journal cover image

Published In

The journal of physical chemistry. A

DOI

EISSN

1520-5215

ISSN

1089-5639

Publication Date

June 2011

Volume

115

Issue

22

Start / End Page

5525 / 5539

Related Subject Headings

  • Thiadiazoles
  • Spectrophotometry, Ultraviolet
  • Quinoxalines
  • Quantum Theory
  • Photons
  • Molecular Structure
  • Fluorescence
  • Electrochemistry
  • 5102 Atomic, molecular and optical physics
  • 3407 Theoretical and computational chemistry