Third-order polarizabilities of symmetric and nonsymmetric polyene and cyanine-like organic molecules

Grant Bourhill; Kamjou Mansour; Bruce G. Tiemann; Christopher B. Gorman; Shawnna Biddle; Seth R. Marder; Joseph W. Perry

doi:10.1117/12.144063

27 April 1993 Third-order polarizabilities of symmetric and nonsymmetric polyene and cyanine-like organic molecules

Grant Bourhill, Kamjou Mansour, Bruce G. Tiemann, Christopher B. Gorman, Shawnna Biddle, Seth R. Marder, Joseph W. Perry

Author Affiliations +

Proceedings Volume 1853, Organic and Biological Optoelectronics; (1993) https://doi.org/10.1117/12.144063
Event: OE/LASE'93: Optics, Electro-Optics, and Laser Applications in Scienceand Engineering, 1993, Los Angeles, CA, United States

Abstract

The second hyperpolarizability, (gamma) , of the donor-acceptor polyene compounds (CH₃)₂N-(CHequalsCH)₃-CHO, 3, (CH₃CH₂CH₂CH₂)₂N- (CHequalsCH)₂-CHequalsC(CN)₂, 4, the cyanine compound [CH₂CH₂OCH₂CH₂-N-(CHequalsCH)₃-CHequalsN-CH₂CH₂OCH₂CH₂]⁺ClO₄^-, 5, and the linear polyenes CH₃- (CHequalsCH)_n-CH₃, where n equals 4, 1, or 5, 2, have been measured by third harmonic generation (THG) at 1907 nm, in a series of solvents ranging in polarity from CCl₄ to CH₃OH. It was found that 3, with the moderately strong formyl acceptor, had positive values of (gamma) which exhibit a peak as a function of solvent polarity. In contrast, 4, with the stronger dicyanovinyl acceptor, had positive (gamma) in very nonpolar solvents but increasingly negative (gamma) values in solvents of moderate to high polarity. These solvent- dependent hyperpolarizabilities are associated with a change in geometry from a highly bond length alternated, polyene-like structure for the formyl-substituted compound in nonpolar solvents, to a cyanine-like structure, with very little bond length alternation, for the dicyanovinyl-substituted compound in polar solvents.

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Grant Bourhill, Kamjou Mansour, Bruce G. Tiemann, Christopher B. Gorman, Shawnna Biddle, Seth R. Marder, and Joseph W. Perry "Third-order polarizabilities of symmetric and nonsymmetric polyene and cyanine-like organic molecules", Proc. SPIE 1853, Organic and Biological Optoelectronics, (27 April 1993); https://doi.org/10.1117/12.144063

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