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Highly Dipolar, Optically Nonlinear Adducts of Tetracyano-p-quinodimethane:  Synthesis, Physical Characterization, and Theoretical Aspects

Szablewski, Marek and Thomas, Philip R. and Thornton, Anna and Bloor, David and Cross, Graham H. and Cole, Jacqueline M. and Howard, Judith A. K. and Malagoli, Massimo and Meyers, Fabienne and Brédas, Jean-Luc and Wenseleers, Wim and Goovaerts, Etienne (1997) Highly Dipolar, Optically Nonlinear Adducts of Tetracyano-p-quinodimethane:  Synthesis, Physical Characterization, and Theoretical Aspects. Journal of the American Chemical Society, 119 (13). pp. 3144-3154. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180517-140738397

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ja963923wDOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ja963923wPublisherSupporting Information
Additional Information:© 1997 American Chemical Society. Received November 12, 1996. Publication Date (Web): April 2, 1997. We thank the U.K. E.P.S.R.C. for support for M.S., A.T., J.M.C., and P.R.T. J.M.C. also receives support from the Institut Laue-Langevin (Grenoble, France). This work was also supported by funds provided under the EU Human Capital and Mobility Programme, Research Network, “Novel third-order nonlinear optical molecular materials” [CHRX-CT93-0334 (DG XII)]. The work in Mons is part funded by the Belgian Federal Government, “Pôle d'Attraction Interuniversitaire en Chimie Supramoleculaire et Catalyse”, FNRS/FRFC, and an IBM Joint Study. We acknowledge the assistance given in NMR studies by Dr. R. S. Matthews. IR spectra were carried out by Mr. Y. Kagawa. The work in Antwerp is part funded by the Flanders Government in its action for the promotion of participation in EU-research programmes and also by the Belgian Fund for Scientific Research (F.W.O.).
Funders:
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)UNSPECIFIED
Institut Laue-LangevinUNSPECIFIED
European UnionCHRX-CT93-0334
Belgian Federal GovernmentUNSPECIFIED
Fonds de la Recherche Scientifique (FNRS)UNSPECIFIED
IBMUNSPECIFIED
Flanders GovernmentUNSPECIFIED
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)UNSPECIFIED
Issue or Number:13
Record Number:CaltechAUTHORS:20180517-140738397
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180517-140738397
Official Citation: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, and, and Etienne Goovaerts. Journal of the American Chemical Society 1997 119 (13), 3144-3154. DOI: 10.1021/ja963923w
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86440
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:18 May 2018 17:09
Last Modified:03 Oct 2019 19:43

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