Journal of Structural Chemistry

, Volume 48, Issue 5, pp 914–921 | Cite as

Molecular and crystal structure of di-and hexamethine merocyanine dyes — derivatives of 3H-indole and malononitrile — manifesting positive solvatochromism

  • A. V. Kulinich
  • A. A. IshchenkoEmail author
  • S. V. Shishkina
  • I. S. Konovalova
  • O. V. Shishkin


Single crystal X-ray diffraction and IR spectroscopy are applied to examine the molecular and crystal structures of 2-[(2E)-2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidine)ethylidene]-malononitrile (1) and 2-[(2E, 4E,6E)-6-2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidine)-2,4-hexadienylidene]-malononitrile (2). It is shown that both in solution and crystalline state the studied merocyanines completely retain the trans-conformation and approach a neutral polyene. It is found that the polyene character is increased in transition from di-to hexamethinemerocyanine, which is caused by a partial violation of conjugation with the nitrogen lone pair due to its slight deviation from the plane of the chromophore. It is demonstrated that the stretching vibration frequency of the nitrile group in the IR spectra of malononitrile merocyanines can be used to examine polyene-polymethine electron relaxations. Electronic and spatial structures of merocyanine molecules are calculated by AM1, PM3, and ab initio methods. Theoretical results are compared to experimental ones.


merocyanines single crystal X-ray diffraction conformation IR spectroscopy quantum chemical calculations 


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  1. 1.
    C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, Wiley-VCH, Weinheim (2003).Google Scholar
  2. 2.
    N. A. Davidenko, A. A. Ishchenko, and H. G. Kuvshinskii, Photonics of Molecular Semiconducting Composites Based on Organic Dyes [in Russian], Naukova dumka, Kiev (2005).Google Scholar
  3. 3.
    A. Mishra, R. K. Behera, P. K. Behera, et al., Chem. Rev., 100, No. 6, 1973–2011 (2000).CrossRefGoogle Scholar
  4. 4.
    R. A. Ganeev, R. I. Tugushev, A. A. Ishchenko, et al., Appl. Phys. B, 76, 683–686 (2003).Google Scholar
  5. 5.
    L. Dalton, A. Harper, A. Ren, et al, Eng. Chem. Res., 38, 8–33 (1999).CrossRefGoogle Scholar
  6. 6.
    I. Baraldi, G. Brancolini, F. Momicchioli, et al, Chem. Phys., 288, 309–325 (2003).CrossRefGoogle Scholar
  7. 7.
    S. L. Bondarev, S. A. Tikhomirov, V. N. Knyukshto, et al., J. Lumin., 124, No. 1, 178–186 (2007).CrossRefGoogle Scholar
  8. 8.
    A. A. Ishchenko, A. V. Kulinich, S. L. Bondarev, et al., Opt. Spectrosc., 101, No. 1, 90–97 (2006).CrossRefGoogle Scholar
  9. 9.
    W.-T. Lim, J.-Zh. Cui, H.-J. Suh, et al., Dyes and Pigments, 56, 7–15 (2003).CrossRefGoogle Scholar
  10. 10.
    A. V. Kulinich, N. A. Derevyanko, and A. A. Ishchenko, Russ. Chem. Bull., 54, No. 12, 2714–2725 (2005).CrossRefGoogle Scholar
  11. 11.
    S. L. Bondarev, S. A. Tikhomirov, V. N. Knyukshto, et al., Opt. Spectrosc., 99, No. 1, 49–55 (2005).CrossRefGoogle Scholar
  12. 12.
    G. M. Sheldrick, SHELXTL PLUS, PC Version, A System of Computer Programs for the Determination of Crystal Structure from X-ray Diffraction Data, Rev. 5.1 (1998).Google Scholar
  13. 13.
    J. J. P. Stewart, J. Computer-Aided Molecular Design, 4, 1–105 (1990).CrossRefGoogle Scholar
  14. 14.
    M. W. Schmidt, K. K. Baldridge, J. A. Boatz, et al., J. Comput. Chem., 14, 1347–1363 (1993).CrossRefGoogle Scholar
  15. 15.
    G. Bach and S. Daehne, Cyanine Dyes and Related Compounds, Rodd’s Chemistry of Carbon Compounds, Vol. IVB, Heterocyclic Compounds (Chapter 15), M. Sainsbury (ed.), Elsevier, Amsterdam (1997), pp. 383–481.Google Scholar
  16. 16.
    A. A. Ishchenko, Structure and Spectral Luminescent Properties of Polymethine Dyes [in Russian], Naukova Dumka, Kiev (1994).Google Scholar
  17. 17.
    G. U. Bublitz, R. Ortiz, S. R. Marder, et al., J. Am. Chem. Soc., 119, No. 14, 3365–3376 (1997).CrossRefGoogle Scholar
  18. 18.
    A. V. Kulinich, A. A. Ishchenko, and U. M. Groth, Spectrochim. Acta, Part A, 68, No. 1, 6–14 (2007).CrossRefGoogle Scholar
  19. 19.
    J. B. Foresman and A. Frish, Exploring Chemistry with Electronic Structure Methods, SE, Gaussian Inc., Pittsburgh (1996).Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • A. V. Kulinich
    • 1
  • A. A. Ishchenko
    • 1
    Email author
  • S. V. Shishkina
    • 2
  • I. S. Konovalova
    • 2
  • O. V. Shishkin
    • 2
  1. 1.Institute of Organic ChemistryNational Academy of Sciences of UkraineKyiv
  2. 2.Scientific Technical Corporation “Institute for Single Crystals”National Academy of Sciences of UkraineKharkov

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