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Electronic stark effect studies of a porphyrin-based push-pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β

Publication ,  Journal Article
Karki, L; Vance, FW; Hupp, JT; LeCours, SM; Therien, MJ
Published in: Journal of the American Chemical Society
March 25, 1998

Electroabsorption or Stark effect spectroscopy has been applied to a pair of porphyrin-based chromophores with the aim of deriving a detailed understanding of the origin of the remarkable first hyperpolarizability, β, of one of the chromophores: [5-[[4'-(dimethylamino)phenyl]ethynyl]-15-[(4- nitrophenyl)-ethynyl]-10,20-diphenylporphinato]zinc(II). The measurements show that significant changes in molecular dipole moment, Δμ, accompany excitations of x-polarized transitions of the aminophenyl (donor)/nitrophenyl (acceptor) functionalized chromophore, but are absent for a related chromophore lacking the donor and acceptor groups. For linear chromophores, changes in dipole moment are a prerequisite to effective molecular first hyperpolarization and incident light frequency doubling behavior. A more detailed consideration of the available |Δμ| data, within the context of a conventional two-level model, has yielded the following: (a) specific information about the roles of each of seven electronic and vibronic excited states in defining β, (b) a semiquantitative explanation for the apparent frequency independence of β found in previous hyper-Rayleigh scattering experiments performed at 830 and 1064 nm, and (c) an explanation for the contrasting frequency dependence of the nonlinear optical response for the analogous Cu(II)-containing chromophore. Finally, the experimental findings are in generally good agreement with published ZINDO calculations which had pointed toward the exceptional effectiveness of yne linkages in coupling donor and acceptor moieties to the highly polarizable porphyrin core assembly.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

March 25, 1998

Volume

120

Issue

11

Start / End Page

2606 / 2611

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Karki, L., Vance, F. W., Hupp, J. T., LeCours, S. M., & Therien, M. J. (1998). Electronic stark effect studies of a porphyrin-based push-pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β. Journal of the American Chemical Society, 120(11), 2606–2611. https://doi.org/10.1021/ja973593v
Karki, L., F. W. Vance, J. T. Hupp, S. M. LeCours, and M. J. Therien. “Electronic stark effect studies of a porphyrin-based push-pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β.” Journal of the American Chemical Society 120, no. 11 (March 25, 1998): 2606–11. https://doi.org/10.1021/ja973593v.
Karki L, Vance FW, Hupp JT, LeCours SM, Therien MJ. Electronic stark effect studies of a porphyrin-based push-pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β. Journal of the American Chemical Society. 1998 Mar 25;120(11):2606–11.
Karki, L., et al. “Electronic stark effect studies of a porphyrin-based push-pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β.” Journal of the American Chemical Society, vol. 120, no. 11, Mar. 1998, pp. 2606–11. Scopus, doi:10.1021/ja973593v.
Karki L, Vance FW, Hupp JT, LeCours SM, Therien MJ. Electronic stark effect studies of a porphyrin-based push-pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β. Journal of the American Chemical Society. 1998 Mar 25;120(11):2606–2611.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

March 25, 1998

Volume

120

Issue

11

Start / End Page

2606 / 2611

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences