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Syntheses and Properties of Two-Dimensional, Dicationic Nonlinear Optical Chromophores Based on Pyrazinyl Cores

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    Syntheses and Properties of Two-Dimensional, Dicationic Nonlinear Optical Chromophores Based on Pyrazinyl Cores
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    † School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom
    ‡ Department of Chemistry, University of Leuven, Celestijnenlaan 200D, B-3001 Leuven, Belgium
    § Molecular Materials Research Center, Beckman Institute, MC 139-74, California Institute of Technology, 1200 East California Boulevard, Pasadena, California 91125, United States
    *To whom correspondence should be addressed. Fax 44 161-275-4598
    [email protected]
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2010, 75, 24, 8550–8563
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    https://doi.org/10.1021/jo101966r
    Published November 16, 2010
    Copyright © 2010 American Chemical Society
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    Abstract

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    Six new dicationic 2D nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by nucleophilic substitutions of 2,6-dichloropyrazine with pyridyl derivatives. These compounds have been characterized as their PF6− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Large red shifts in the intense, π → π* intramolecular charge-transfer (ICT) transitions on replacing −OMe with −NMe2 substituents arise from the stronger π-electron donor ability of the latter. Each compound shows a number of redox processes which are largely irreversible. Single crystal X-ray structures have been determined for five salts, including two nitrates, all of which adopt centrosymmetric packing arrangements. Molecular first hyperpolarizabilities β have been determined by using femtosecond hyper-Rayleigh scattering at 880 and 800 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly 2D, with dominant “off-diagonal” βzyy components. Stark (electroabsorption) spectroscopic measurements on the ICT bands afford estimated static first hyperpolarizabilities β0. The directly and indirectly derived β values are large, and the Stark-derived β0 response for one of the new salts is several times greater than that determined for (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium hexafluorophosphate. These Stark spectroscopic studies also permit quantitative comparisons with related 2D, binuclear RuII ammine complex salts.

    Copyright © 2010 American Chemical Society

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    Crystallographic information in CIF format and 1H and 13C NMR spectra. This material is available free of charge via the Internet at http://pubs.acs.org.

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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2010, 75, 24, 8550–8563
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo101966r
    Published November 16, 2010
    Copyright © 2010 American Chemical Society
    Request reuse permissions

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