Highly dipolar, optically nonlinear adducts of tetracyano-p-quinodimethane: Synthesis, physical characterization, and theoretical aspects

Marek Szablewski, Philip R. Thomas, Anna Thornton, David Bloor*, Graham H. Cross, Jacqueline M. Cole, Judith A.K. Howard, Massimo Malagoli, Fabienne Meyers, Jean Luc Brédas, Wim Wenseleers, Etienne Goovaerts

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

118 Scopus citations

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 x 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.

Original languageEnglish (US)
Pages (from-to)3144-3154
Number of pages11
JournalJournal of the American Chemical Society
Volume119
Issue number13
DOIs
StatePublished - Apr 2 1997

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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