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Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores.

Publication ,  Journal Article
Uyeda, HT; Zhao, Y; Wostyn, K; Asselberghs, I; Clays, K; Persoons, A; Therien, MJ
Published in: Journal of the American Chemical Society
November 2002

The syntheses and electrooptic properties of a new family of nonlinear optical chromophores are reported. These species feature an ethyne-elaborated, highly polarizable porphyrinic component and metal polypyridyl complexes that serve as integral donor and acceptor elements. Examples of this structural motif include ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)(2+) bis-hexafluorophosphate (Ru-PZn); osmium(II) [5-(4'-ethynyl-(2,2';6',2''-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2''-terpyridine)(2+) bis-hexafluorophosphate (Os-PZn); ruthenium(II) [5-(4'-ethynyl-(2,2';6',2''-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phen-yl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)(2+) bis-hexafluorophosphate (Ru-PZn-A); osmium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)(2+) bis-hexafluorophosphate (Os-PZn-A); and ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))osmium(II)-15-(4'-ethynyl-(2,2';6',2''-terpyridinyl))-10,20-bis (2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-bis(2,2';6',2''-terpyridine)(4+) tetrakis-hexafluorophosphate (Ru-PZn-Os). The frequency dependence of the dynamic hyperpolarizability of these compounds was determined from hyperRayleigh light scattering (HRS) measurements carried out at fundamental incident irradiation wavelengths (lambda(inc)) of 800, 1064, and 1300 nm. These data show that (i) coupled oscillator photophysics and metal-mediated cross-coupling can be exploited to elaborate high beta(0) supermolecules that exhibit significant excited-state electronic communication between their respective pigment building blocks; (ii) high-stability metal polypyridyl compounds constitute an attractive alternative to electron releasing dialkyl- and diarylamino groups, the most commonly used donor moieties in a wide range of established nonlinear optical dyes; (iii) this design strategy enables ready elaboration of chromophores having extraordinarily large dynamic hyperpolarizabilities (beta(lambda) values) at telecommunication relevant wavelengths; and (iv) porphyrin B- and Q-state-derived static hyperpolarizabilities (beta(0) values) can be designed to have the same or opposite sign in these species, thus providing a new means to regulate the magnitude of lambda(inc)-specific dynamic hyperpolarizabilities.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

November 2002

Volume

124

Issue

46

Start / End Page

13806 / 13813

Related Subject Headings

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

Citation

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Uyeda, H. T., Zhao, Y., Wostyn, K., Asselberghs, I., Clays, K., Persoons, A., & Therien, M. J. (2002). Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores. Journal of the American Chemical Society, 124(46), 13806–13813. https://doi.org/10.1021/ja020651q
Uyeda, H Tetsuo, Yuxia Zhao, Kurt Wostyn, Inge Asselberghs, Koen Clays, André Persoons, and Michael J. Therien. “Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores.Journal of the American Chemical Society 124, no. 46 (November 2002): 13806–13. https://doi.org/10.1021/ja020651q.
Uyeda HT, Zhao Y, Wostyn K, Asselberghs I, Clays K, Persoons A, et al. Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores. Journal of the American Chemical Society. 2002 Nov;124(46):13806–13.
Uyeda, H. Tetsuo, et al. “Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores.Journal of the American Chemical Society, vol. 124, no. 46, Nov. 2002, pp. 13806–13. Epmc, doi:10.1021/ja020651q.
Uyeda HT, Zhao Y, Wostyn K, Asselberghs I, Clays K, Persoons A, Therien MJ. Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores. Journal of the American Chemical Society. 2002 Nov;124(46):13806–13813.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

November 2002

Volume

124

Issue

46

Start / End Page

13806 / 13813

Related Subject Headings

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