Octupolar oligomers containing 2-12 molecules of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives have been synthesized and their nonlinear optical and two-photon absorption (TPA) properties were determined. The beta(0) values are in the range of (85-1219) x 10(-30) esu and increase monotonically with the increasing number of the octupolar units within the molecule. The two-photon-induced fluorescence excitation spectra are quite similar to the single-photon absorption spectra except that the wavelength is doubled, indicating that the one- and two-photon allowed excited states are the same. The peak TPA cross-section values (delta(max)) measured with nanosecond pulses by the two-photon-induced fluorescence method are in the range (3010-62, 930) x 10(-50) cm(4)s photon(-1). The delta(max) increases as the number of the octupolar units in the molecules increases. A linear relationship is observed between delta(max) and beta, and this delta-beta relationship serves as a useful design strategy for the synthesis of novel octupolar oligomers and polymers with large TPA and beta.
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http://dx.doi.org/10.1002/1521-3765(20020902)8:17<3907::AID-CHEM3907>3.0.CO;2-F | DOI Listing |
Chemistry
November 2006
Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, 5000 Namur, Belgium.
The structure and second-order nonlinear optical properties of a series of helical pyridine-pyrimidine oligomers recently synthesized by Barboiu and Lehn have been investigated theoretically by combining molecular mechanics and quantum chemistry approaches. In the absence of substituents, the hyper-Rayleigh scattering response (betaHRS) and the projection of the first hyperpolarizability on the dipole moment (beta||) exhibit periodic variations with chain length, but these nonlinear optical responses remain small. The first hyperpolarizabilities can, however, be enhanced by adding substituents.
View Article and Find Full Text PDFChemistry
September 2002
Department of Chemistry and Center for Electro- and Photo-Responsive Molecules, Korea University, Seoul.
Octupolar oligomers containing 2-12 molecules of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives have been synthesized and their nonlinear optical and two-photon absorption (TPA) properties were determined. The beta(0) values are in the range of (85-1219) x 10(-30) esu and increase monotonically with the increasing number of the octupolar units within the molecule. The two-photon-induced fluorescence excitation spectra are quite similar to the single-photon absorption spectra except that the wavelength is doubled, indicating that the one- and two-photon allowed excited states are the same.
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