Publication
Title
Highly dipolar, optically nonlinear adducts of tetracyano-**p**-quinodimethane: synthesis, physical characterization, and theoretical aspects
Author
Abstract
A new series of nonlinear optical molecules are described where the ground state polarization is predominantly zwitterionic when the molecules are dissolved in solution. The molecules, which are derived in general from facile reactions between tertiary amines and tetracyano-p-quinodimethane (TCNQ), are of a type where the stabilization of the charge-separated ground state is favored by an increase in aromaticity over the neutral, quinoidal forms of the molecules. The measured second-order optical nonlinearity of one in the series has been measured by hyper-Rayleigh scattering and a figure of merit value, μβ(0), being the product of the dipole moment and static first hyperpolarizability, is found to be 9500 × 10-48 esu. This value, which is higher than most other reported values, is taken from studies in chlorinated solvents of relatively low polarity, but the discussion emphasizes the evolution of μβ(0) with solvent polarity, showing that even higher values could be expected with only modest increases in the polarity of the surrounding medium. The analysis of experimental data taken during dipole moment studies is thoroughly examined, and it is concluded that full account must be taken of the molecular shape to correlate the results with theoretical calculations. An ellipsoidal reaction field model is preferred for these highly one-dimensional molecules having strongly anisotropic polarizabilities.
Language
English
Source (journal)
Journal of the American Chemical Society. - Washington, D.C., 1879, currens
Publication
Washington, D.C. : American Chemical Society , 1997
ISSN
0002-7863
DOI
10.1021/JA963923W
Volume/pages
119 :13 (1997) , p. 3144-3154
ISI
A1997WR15000021
Full text (Publisher's DOI)
UAntwerpen
Faculty/Department
Publication type
Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
Identifier
Creation 08.10.2008
Last edited 04.03.2024
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