Visn. Nac. Akad. Nauk Ukr. 2017. (11): 30-42

A.A. Ishchenko
Institute of Organic Chemistry of NAS of Ukraine, Kyiv

According to the materials of scientific report at the meeting of the Presidium of NAS of Ukraine, September 27, 2017

Regularities that connect the photonic properties of polymethine dyes with their structure and medium nature are considered. Particular attention is paid to non-trivial effects: violation of the classical law of the mirror symmetry of absorption and fluorescence spectra; unusual solvatochromism of symmetric dyes; approximation of typical electron-asymmetric dyes in the excited state to symmetric, which causes a record increase of Stokes shift; dependences of photophysical and nonlinear-optical properties of polymethines on the nature of uncolored counterion. The factors that determine them are analyzed. Examples of practical application of the developed polymethines in laser technology, nonlinear optics, holography, photovoltaics, electroluminescence and photodynamic therapy are given. Features of their structure, providing the possibility of using polymethines in these areas, are interpreted.
Keywords: polymethine dyes, electronic structure, spectral luminescent and nonlinear optical properties, solvatochromism, aggregation, laser, holographic, photovoltaic and electroluminescent media.

Language of article: ukrainian



  1. Kiprianov A.I. Colour and structure of cyanine dyes. (Kyiv: Naukova Dumka, 1959).
  2. James T.H. The Theory of the Photographic Process. (New York: Macmillan Pub. Co., 1977).
  3. Tolmachev A.I., Slominskii Yu.L., Ishchenko A.A. New cyanine dyes absorbing in the NIR region (review). NATO ASI Series. 3. (Eds. S. Daehne, U. Resch-Genger, O.S. Wolfbeis). (Dordrecht–Boston–London: Kluwer Academic Publishers, 1998). V. 52. P. 385-415.
  4. Ishchenko O.O., Slominskii Y.l., Tolmachev O.I. Modern achievements in the field of polymethine dyes of A.I. Kiprianov’s school. Journal of Organic and Pharmaceutical Chemistry. 2009. 7(3): 3.
  5. Il’chenko A.Ya. The fundamentals of the theory of organic dyes chromaticity. (Kyiv: Naukova Dumka, 2012).
  6. Ishchenko A.A. Laser media based on polymethine dyes (Reviews). Quantum Electronics. 1994. 24(6): 471.
  7. Ishchenko A.A. Structure and spectral-luminescent properties of polymethine dyes. (Kyiv: Naukova Dumka, 1994).
  8. Vavilov S.I. About photoluminescence of solutions. Bulletin of the Russian Academy of Sciences. Physics. 1945. 9(4/5): 283.
  9. Kulinich A.V., Derevyanko N.A., Ishchenko A.A., Bondarev S.L., Knyukshto V.N. Structure and fluorescence properties of indole cyanine and merocyanine dyes with partially locked polymethyne chain. J. Photochem. Photobiol. A. 2008. 200(2-3): 106.
  10. Kulinich A.V., Derevyanko N.A., Ishchenko A.A. Synthesis and spectral properties of cyanine dyes – derivatives of 10,10-dimethyl-7,8,9,10-tetrahydro-6H-pyrido[1,2-a]indolium. J. Photochem. Photobiol. A. 2008. 198(2-3): 119.
  11. Kulinich A.V., Ishchenko A.A. Merocyanine dyes: synthesis, structure, properties, application. Russ. Chem. Rev. 2009. 78(2): 141.
  12. Kulinich A.V., Derevyanko N.A., Ishchenko A.A. Synthesis and spectral properties of malononitrile-based merocyanine dyes. Russ. Chem. Bull. 2005. 54(12): 2820.
  13. Kulinich A.V., Derevyanko N.A., Ishchenko A.A. Synthesis, Structure, and Solvatochromism of Merocyanine Dyes Based on Barbituric Acid. Russ. J. Gen. Chem. 2006. 76(9): 1441.
  14. Ishchenko A.A., Kulinich A.V., Bondarev S.L., Knyukshto V.N. Structure and Fluorescence Properties of Merocyanine Dyes Derived from Dimethylbarbituric Acid. Russ. J. Gen. Chem. 2007. 77(10): 1787.
  15. Kulinich A.V., Derevyanko N.A., Ishchenko A.A. Electronic structure and solvatochromism of merocyanines based on N,N-diethylthiobarbituric acid. J. Photochem. Photobiol. A. 2007. 188: 207.
  16. Kulinich A.V., Ishchenko A.A., Groth U.M. Electronic structure and solvatochromism of merocyanines NMR spectroscopic point of view. Spectrochim. Acta. Part A. 2007. 68(1): 6.
  17. Ishchenko A.A., Kulinich A.V., Bondarev S.L., Knyukshto V.N. Photodynamics of Polyene-Polymethine Transformations and Spectral Fluorescent Properties of Merocyanine Dyes. J. Phys. Chem. A. 2007. 111(51): 13629.
  18. Ishchenko A.A., Kulinich A.V., Bondarev S.L., Knyukshto V.N. Electronic Structure and Fluorescent Properties of Malononitrile-Based Merocyanines with Positive and Negative Solvatochromism. Optics and Spectroscopy. 2008. 104(1): 57.
  19. Kulinich A.V., Ishchenko A.A., Chibisov A.K., Zakharova G.V. Effect of electronic asymmetry and the polymethine chain length on photoprocesses in merocyanine dyes. J. Photochem. Photobiol. A. 2014. 274: 91.
  20. Ibrayev N.Kh., Yeroshina S.A., Ishchenko A.A., Mushkalo I.L. Investigation of cоnfоrmаtiопal and electron properties of biscyanine dyes. Mol. Cryst. Liq. Cryst. 2005. 427: 139.
  21. Ibraev N.Kh., Ishchenko A.A., Karamysheva R.Kh., Mushkalo I.L. Influence of interaction of chromophores, linked by the unconjugated chain, on the luminescence properties of biscyanine dyes. J. Luminescence. 2000. 90(3-4): 81.
  22. Ishchenko A.A., Derevyanko N.A., Svidro V.A. Constitution and fluorescence spectra of unsymmetrical polymethine dyes. Dyes and Pigments. 1992. 19(3): 169.
  23. Ishchenko A.A. Structure and spectral-luminescent properties of polymethine dyes. Russ. Chem. Rev. 1991. 60(8): 865.
  24. Derevyanko N.A., Ishchenko A.A., Slominski Yu.L., Tolmachev A.I. First examples of dyes of the pyridopyrylo- and pyridopolycarbocyanine series: Synthesis and special spectral-luminescent properties. Mendeleev Communications. 1991. 1(3): 91.
  25. Svetlichnyi V.A., Bazyl O.K., Kashapova E.R., Derevyanko N.A., Ishchenko A.A. Influence of absorption from excited singlet states on the lasing parameters of polymethine dyes. Quantum Electronics. 2009. 39(8): 739.
  26. Ishchenko A.A. Molecular Engineering of Dye-doped Polymers for Optoelectronics. Polym. Adv. Technol. 2002. 13(10-12): 744.
  27. Bliznyuk V.N., Seliman A.F., Ishchenko A.A., Derevyanko N.A., DeVol T.A. New Efficient Organic Scintillators Derived from Pyrazoline. ACS Appl. Mater. Interfaces. 2016. 8(20): 12843.
  28. Voiciuk V., Redeckas K., Derevyanko N.A., Kulinich A.V., Barkauskas M., Vengris M., Sirutkaitis V., Ishchenko A.A. Study of photophysical properties of a series of polymethine dyes by femtosecond laser photolysis. Dyes and Pigments. 2014. 109: 120.
  29. Kulinich A.V., Derevyanko N.A., Mikitenko E.K., Ishchenko A.A. Merocyanines based on 1,3-indanedione: electronic structure and solvatochromism. J. Phys. Org. Chem. 2011. 24(8): 732.
  30. Bondarev S.L., Tikhomirov S.A., Knyukshto V.N., Turban A.A., Ishchenko A.A., Kulinich A.V., Ledoux I. Fluorescence and solvatochromism of a merocyanine dye with a high quadratic polarizability in solutions and polymer films. Journal of Luminescence. 2007. 124(1): 178.
  31. Svetlichnyi V.A., Ishchenko A.A., Vaitulevich E.A., Derevyanko N.A., Kulinich A.V. Nonlinear optical characteristics and lasing ability of merocyanine dyes having different solvatochromic behaviour. Optics Communications. 2008. 281: 6072.
  32. Ganeev R.A., Tugushev R.I., Ishchenko A.A., Derevyanko N.A., Ryasnyansky A.I., Usmanov T. Characterization of nonlinear optical parameters of polymethine dyes. Appl. Phys. B. 2003. 76: 683.
  33. Svetlichnyi V.A., Kopylova T.N., Mayer G.V., Lapin I.N., Derevyanko N.A., Ishchenko A.A. Photonics of laser-excited symmetric cationic polymethine dyes. Quantum Electronics. 2007. 37(2): 118.
  34. Kulinich A.V., Mikitenko E.K., Ishchenko A.A. Scope of negative solvatochromism and solvatofluorochromism of merocyanines. Phys. Chem. Chem.Phys. 2016. 18(5): 3444.
  35. Ishchenko A.A., Derevyanko N.A., Zubarovskii V.M., Tolmachev A.I. Influence of length of the polymethine chain on width of absorption bands of symmetric cyanine dyes. Theoret. Experim. Chem. 1984. 20(4): 415.
  36. Derevyanko N.A., Ishchenko A.A., Kuchma I.G., Mak A.A., Murzin A.G., Pivinskii E.G., Prilezhaev D.S., Slominsky Yu.L., Smirnova Z.A., Tolmachev A.I., Fromzel V.A. Fast passive switch based on polymethine dyes for erbium laser with 1.54 μm wavelength. Optics and Spectroscopy (Optika i Spektroskopiya). 1989. 67(4): 920.
  37. Derevyanko N.A., Dyadyusha G.G., Ishchenko A.A., Tolmachev A.I. Influence of nature of solvent on position, intensity, and shape of absorption bands of polymethine dyes. Theoret. Experim. Chem. 1983. 19(2): 150.
  38. Fromzel V., Ishchenko A., Kuchma I., Murzin A., Pivinsky E., Prilegaev D. New quickly relaxing dye for passive mode-locking at 1300–1750 nm. Proc. SPIE. 1992. 1842: 56.
  39. Kurdyukova I.V., Derevyanko N.A., Ishchenko A.A., Mysyk D.D. Deeply colored anionic polymethine dyes derived from bis(2,2,3,3,4,4,5,5-octafluoropentyl)-9H-fluorene-2,7-disulfonate. Russ. Chem. Bull. 2009. 58(4): 828.
  40. Kurdiukova I.V., Kulinich A.V., Ishchenko A.A. Near-infrared squarate and croconate dianions derived from tetranitrofluorene. New Journal of Chemistry. 2012. 36(8): 1564.
  41. Kurdyukova I.V., Ishchenko A.A., Mysyk D.D. Synthesis and spectral properties of near-IR polymethine dyes derived from tris(2,2,3,3,4,4,5,5-octafluoropentyl)-9H-fluorene-2,4,7-trisulfonate. Dyes and Pigments. 2017. 142: 201.
  42. Ishchenko A.A. Svidro V.A., Derevyanko N.A. Solvatofluorochromy of cationic cyanine dyes. Dyes and Pigments. 1989. 10(2): 85.
  43. Ishchenko A.A., Dokukina A.F., Smirnova Z.A., Tolmachev A.I. Chemical structure and form of absorption bands of polymethine dyes in the polymer matrix. Dokl. Akad. Nauk SSSR. 1985. 284(6): 1407.
  44. Ishchenko A.A. Photonics and molecular design of dye-doped polymers for modern light-sensitive materials. Pure Appl. Chem. 2008. 80(7): 1525.
  45. Bezrodnyi V.I., Ishchenko A.A.. High-energy single pulse and multispike operation with a passive polymer Q-switch. Optics and Laser Technology. 2002. 34(1): 7.
  46. Bezrodnyi V.I., Ishchenko A.A. High efficiency lasing of the dye-doped polymer laser with 1.06 mm pumping. Appl. Phys. B. 2001. 73(3): 283.
  47. Bezrodnyi V.I., Derevyanko N.A., Ishchenko A.A., Karabanova L.V., Plisko T.A., Slominskii Yu.L., Smirnova A.L. Absorption filters based on polymethine dyes for protection from laser radiation with a wavelength of 1060 nm. J. Optical Technology. 1996. 63(12): 936.
  48. Grabchuk G.P.. Ishchenko A.A,, Kolendo A.Yu. Influence of Cationic Symmetric Polymethine Dyes on Radical Polymerization of Methylmethacrylate in Solution. Mol. Cryst. Liq. Cryst. 2008. 485: 817.
  49. Grabchuk G.P., Kolendo A.Yu., Derevyanko N.A., Ishchenko A.A. Effect of a Structure of Polymethine Dyes on the Methyl Methacrylate Free Radical Polymerization in a Solution. Mol. Cryst. Liq. Cryst. 2011. 536: 130.
  50. Bulavko G.V., Ishchenko A.A. Organic bulk heterojunction photovoltaic structures: design, morphology and properties. Russ. Chem. Rev. 2014. 83(7): 575.
  51. Malyukin Yu.V., Ishchenko A.A., Tovmachenko O.G. Spectroscopy of exciton traps in J-aggregates of quino-2-monomethinecyanine. Optics and Spectroscopy. 1996. 80(1): 84.
  52. Barashkov N., Irgibayeva I., Aldongarov A., Mantel A., Ishchenko A., Sakhno T. Investigation of two alternative methods of introducing fluorescent dyes in the Au nanoparticles-polysiloxane composites. 249th ACS National Meeting (Denver, CO, USA). 2015. P. 421.
  53. Reisfeld R., Weiss A., Saraidarov T., Yariv E., Ishchenko A.A. Solid-state lasers based on inorganic–organic hybrid materials obtained by combined sol–gel polymer technology (Review). Polym. Adv. Technol. 2004. 15(10-12): 1.
  54. Fenenko L.I., Ishchenko A.A., Verbitsky A.B., Vertsimakha Ya.I. Photovoltaic effects in composites of V2O5 xerogel with polymethine dyes. Mol. Cryst. Liq. Cryst. 2005. 426: 157.
  55. Kobasa I., Odosiy L., Kurdyukova I., Ishchenko O., Kurek S. Electrochemical and energetic characteristics of new dye-sensitizers for photovoltaic cells. Funct. Mater. Lett. 2015. 8(5): 1550067.
  56. Ibrayev N.Kh., Seliverstova E.V., Ishchenko A.A., Kudinova M.A.. The effect of sulfonate groups on spectral-luminescent and photovoltaic properties of squarylium dyes. J. Photochem. Photobiol. A. 2017. 346: 570.
  57. Derevyanko N.O., Ishchenko O.O., Kulinich A.V., Sharanda L.F., Shul’ga S.V., Ogenko V.M. Interaction of polymethine dyes of different ion and nano-carbon structures. Nanosistemi, Nanomateriali, Nanotehnologii. 2017. 15(2): 337.
  58. Dyadyusha G.G., Ishchenko A.A., Derevyanko N.A., Tolmachev A.I. Study of ionic equilibria of indotricarbocyanines in aromatic hydrocarbons. Dokl. Akad. Nauk SSSR. 1982. 264(2): 351.
  59. Tatikolov A.S., Dzhulibekov Kh.S., Shvedova L.A., Kuzmin V.A., Ishchenko A.A. Influence of “inert” counterions on the photochemistry of some cationic polymethine dyes. J. Phys. Chem. 1995. 99(17): 6525.
  60. Tatikolov A.S., Shvedova L.A., Derevyanko N.A., Ishchenko A.A., Kuzmin V.A. The influence of counterion on photochemistry of cationic indopolycarbocyanine dyes in ion pairs. Chem. Phys. Lett. 1992. 190(3-4): 291.
  61. Tatikolov A.S., Derevyanko N.A., Ishchenko A.A., Baraldi I., Caselli M., Momicchioli F., Ponterini G. Photoisomerization of asymmetric indobenzimidazolocyanine dyes. Ber. Bunsenges. phys. Chem. 1995. 99(5): 763.
  62. Demchuk M.I., Ishchenko A.A., Mikhailov V.P., Avdeeva V.I. The influence of the anion on the excited-state relaxation time of cationic polymethine dyes. Chem. Phys .Lett. 1988. 144(1): 99.
  63. Demchuk M.I., Ishchenko A.A., Krasnaya Zh.A., Mikhailov V.P. The excited-state relaxation times of cationic-anionic polymethine dyes. Chem. Phys. Lett. 1990. 167(1-2): 170.
  64. Davidenko N.A., Ishchenko A.A. Spin conversion and electric field effect on photoluminescence in amorphous molecular semiconductors doped with ionic dyes. Chem. Phys. 1999. 247: 237.
  65. Ishchenko A.A., Derevyanko N.A., Vinogradov A.M. Photoinduced Electron Transfer in Ion Pairs of Indotricarbocyanine Dyes. Russ. J. Gen. Chem. 1997. 67(7): 1122.
  66. Bulavko G.V., Davidenko N.A., Derevyanko N.A., Ishchenko A.A. Effects of the Nature of the Anion of Cationic Polymethine Dyes on the Photovoltaic Properties of Polymer Photosemiconductor Composites. High Energy Chemistry. 2015. 49(5): 331.
  67. Kaplevskii K.L. Symmetric indotricarbocyanine dyes in solutions and biological structures: ionic equilibrium, photonics, photocytotoxicity. PhD Thesis (Optics). (Minsk, 2005).
  68. Davidenko N.A., Ishchenko A.A., Kuvshinski N.G. Photonics of Molecular Semiconductor Composites Based on Organic Dyes. (Kyiv: Naukova Dumka, 2005).
  69. Davidenko N.A., Ishchenko A.A., Kulinich A.V., Studzinsky S.L. Effect of concentration of anionic polymethine dye in poly-N-epoxypropylcarbazole polymer film composite on the spectral-luminescent properties and photoconductivity. Spectrochim. Acta A. 2012. 98(12): 271.
  70. Bulavko G.V., Davidenko N.A., Shkavro A.G., Tretyak O.V., Ishchenko A.A., Kulinich A.V. Photovoltaic effect in dye-doped polymer films with free-surface and sandwich structures. Funct. Mater. Lett. 2017. 10(2): 1750007.
  71. Davidenko N., Davidenko I., Ishchenko A., Kulinich A., Pavlov V., Studzinsky S., Chuprina N. Reversible holographic recording media based on polymeric composites and their use in energy-saving technologies. Applied Optics. 2012. 51(10): C49.
  73. Bliznyuk V.N., Gasiorowski J., Ishchenko A.A., Bulavko G.V., Derevyanko N.A., Sariciftci N.S. Photoresistance and photoinduced current hysteresis in bulk heterojunction systems P3HT-PCBM-polymethine dye. Organic Electronics. 2014. 15(6): 1105.
  74. Bliznyuk V.N., Gasiorowski J., Ishchenko A.A., Bulavko G.V., Rahaman M., Hingerl K., Zahn D.R.T., Sariciftci N.S. Photovoltaic cells based on ternary P3HT:PCBM:polymethine dye active layer transparent in the visible range of light. Appl. Surf. Sci. 2016. 389: 419.
  75. Davidenko N.A., Ishchenko A.A. Electroluminescence of New Dyed Polymer Films in Sandwich Structures. Tech. Phys. Lett. 2002. 28(6): 483.
  76. Ishchenko A. Photo-Converters Based on Dye-Doped Polymers. In: Specialty Polymers. Materials and Applications (Ed. Faiz Mohammad), (New Delhi–Bangalore–Mumbai: I.K. International Publishing House Pvt. Ltd.. 2007). P. 301-356.
  77. Manzhara V.S., Fedorovich R.D., Verbitsky A.B., Kulinich A.V., Ishchenko A.A. Photo- and electroluminescence of merocyanine dye M-440. Mol. Cryst. Liq. Cryst. 2005. 426: 303.