Skip to main content

Research Repository

Advanced Search

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

Szablewski, M.; Thomas, P.R.; Thornton, A.; Bloor, D.; Cross, G.H.; Cole, J.M.; Howard, J.A.K.; Malagoli, M.; Meyers, F.; Bredas, J.L.; Wenseleers, W.; Goovaerts, E.

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


Authors

P.R. Thomas

A. Thornton

D. Bloor

G.H. Cross

J.M. Cole

J.A.K. Howard

M. Malagoli

F. Meyers

J.L. Bredas

W. Wenseleers

E. Goovaerts



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.

Journal Article Type Article
Publication Date Apr 2, 1997
Deposit Date May 29, 2015
Publicly Available Date Jun 5, 2015
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 119
Issue 13
Pages 3144-3154
DOI https://doi.org/10.1021/ja963923w
Public URL https://durham-repository.worktribe.com/output/1523736

Files

Accepted Journal Article (243 Kb)
PDF

Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ja963923w.






You might also like



Downloadable Citations