Skip to main content
SpringerLink
Log in

Spectral Properties of Y-Shaped Donor-Acceptor Push-Pull Imidazole-based Fluorophores: Comparison between Solution and Polymer Matrices

  • ORIGINAL PAPER
  • Published:
Journal of Fluorescence Aims and scope Submit manuscript

Abstract

The spectral properties of a novel type of Y-shaped fluorophores consisting of an imidazole ring end-capped with two electron-donating N,N-dimethylaminophenyl groups at positions C4 and C5 and one electron-withdrawing cyano group on the imidazole moiety at position C2 were examined. The π-linker separating the 4,5-bis[4-(N,N-dimethylamino)phenyl]-1H-imidazole donor moiety and the cyano group comprises 1,4-phenylene (1), (E)-phenylethenyl (2), (E)-phenylbuta-1,3-dienyl (3), biphenyl (4), (E)-phenylethenylphenyl (5) and phenylethynylphenyl (6) conjugated paths. The absorption and fluorescence spectra were obtained in toluene, dichloromethane, acetonitrile and methanol and in polymer matrices such as polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(vinylchloride) (PVC). The most intense absorption bands of fluorophores 1–6 were observed within the range of 283 to 330 nm. Less intense but longer-wavelength absorption bands designated as charge-transfer bands were observed at approximately 380–430 nm depending on the medium. The fluorophores exhibited strong fluorescence in the visible region with a Stokes shift of approximately 4300–5800 cm−1 in non-polar toluene and polystyrene, whereas very low intensity of fluorescence was observed with a Stokes shift in the 6500–7800 cm−1 region in polar methanol and acetonitrile. The large Stokes shift indicates a large difference in the spatial arrangement of the chromophore in the absorbing and emitting states. A relatively intense fluorescence (quantum yields of 0.12–0.69) was observed only for derivative 1 in all media except methanol. The fluorophores doped in matrices yielded more intense fluorescence compared with the fluorescence in liquid media. The use of solid polymer matrices lowers the probability of forming non-emissive excited states. The fluorescence lifetimes were short (1–4 ns) for all of the fluorophores in solvents and in polymer matrices.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Jen AK-Y, Yue Zhang (1998) Electronoptic Polymers and Applications; Materials Based on Heteroaromatic Nonlinear optical Chromophores in Photonic Polymer Systems: Fundamentals, Methods and Applications, Eds.: Wise DL, Wnek GC, Trantolo DJ, Cooper TM, Gresser JD, Macel Dekker Inc. 270 Madison Avenue, New York, NY 10016–0602, Ch. 21 pp 847

  2. Special issue on Organic Electronics and Optoelectronics, (2007), (Eds. S. R. Forrest, M. E. Thompson). Chem Rev 107:923–1386

    Google Scholar 

  3. Special issue on Materials for electronics, (2010), (Eds. R. D. Miller, E. A. Chandross), Chem Rev 110: 1–574

    Google Scholar 

  4. Special issue on Organic Photovoltaics, (2009), (Eds.: J. L. Brédas, J. R. Durrant), Acc Chem Res 42: 1689–1857

    Google Scholar 

  5. Grabowski ZM (1993) Electron transfer in flexible molecules and molecular ions. Pure Appl Chem 65:1751–1756. doi:10.1351/pac199365081751

    Article  CAS  Google Scholar 

  6. Safarzadeh-Amiri A (1986) A time resolved fluorescence study of dynamic stokes shift of trans-4-dimethylamino-4′-cyanostilbene. Chem Phys Lett 125:272–278. doi:10.1016/0009-2614(86)87063-4

    Article  CAS  Google Scholar 

  7. Abdel-Mottaleb MSA, Loufty RO, Laouyade R (1989) Non-radiative deactivation channels of molecular rotors. J Photochem Photobiol A 48:87–93. doi:10.1016/1010-6030(89)87093-5

    Article  CAS  Google Scholar 

  8. Mqadmi S, Pollet A (1990) Non-radiative deactivation of p-(N, N-dialkylamino)- benzylidenemalonitriles. J Photochem Photobiol A 53:275–281. doi:10.1016/1010-6030(90)87131-T

    Article  CAS  Google Scholar 

  9. Paczkowski J, Neckers DC (1991) The nature of the ground and excited states of substituted (N, N-dialkylamino)cinnamated and banzalmalonate. J Photochem Photobiol A 62:173–181. doi:10.1016/1010-6030(91)87018-Q

    Article  CAS  Google Scholar 

  10. Wang SL, Ho TI (2000) Substituent effects on intramolecular charge-transfer behaviour of styrylheterocycles. J Photochem Photobiol A 135:119–126. doi:10.1016/S1010-6030(00)00289-6

    Article  CAS  Google Scholar 

  11. Yesodha SK, Pillai ChKS, Tsutsumi N (2004) Stable polymeric materials for nonlinear optics: a review based on azobenzene systems. Prog Polym Sci 29:45–74. doi:10.1016/j.progpolymsci.2003.07.002

    Article  CAS  Google Scholar 

  12. Bureš F, Schweizer WB, May JC, Boudon C, Gisselbrecht J-P, Gross M, Biaggio I, Diederich F (2007) Property tuning in charge transfer chromophores by systematic modulation of the spacer between donor and acceptor. Chem Eur J 13:5378–5387. doi:10.1002/chem.200601735

    Article  PubMed  Google Scholar 

  13. Wu YL, Bureš F, Jarowski PD, Schweizer WB, Boudon C, Gisselbrecht J-P, Diederich F (2010) Proaromacity: Organic charge–transfer chromophores with Smaal HOMO-LUMO gaps. Chem Eur J 16:9592–9605. doi:10.1002/chem.201001051

    Article  PubMed  CAS  Google Scholar 

  14. Bureš F, Schweizer WB, May JC, Boudon C, Gisselbrecht J-P, Gross M, Diederich F (2008) New push-pull chromophores featuring TCAQ (11,11,12,12-tetracyano-9,10-anthraquinodimethanes) and other dicyanovinyl acceptors. Eur J Org Chem 994–1004. doi:10.1002/ejoc.200700970

  15. Bureš F, Pytela O, Diederich F (2009) Solvent effects on electronic absorption spectra of donor substituted 11,11,12,12-tetracyano-9,10-anthraquinodimethanes (TCAQs). J Phys Org Chem 22:155–162. doi:10.1002/poc.1443

    Article  Google Scholar 

  16. Bureš F, Pytela O, Kivala M, Diederich F (2011) Solvatochromism as an efficient tool to study N, N-Dimethylamino- and Cyano-substituted π-conjugated molecules with an intramolecular charge-transfer absorption. J Phys Org Chem 24:274–281. doi:10.1002/poc.1744

    Article  Google Scholar 

  17. Kulhánek J, Bureš F, Pytela O, Mikysek T, Ludvík J, Růžička A (2010) Push - pull molecules with a systematically extended π-conjugated system featuring 4,5-dicyanoimidazole. Dyes Pigm 85:57–65. doi:10.1016/j.dyepig.2009.10.004

    Article  Google Scholar 

  18. Bureš F, Kulhánek J, Mikysek T, Ludwig J, Lokaj J (2010) Branched charge transfer chromophores featuring a 4,5-dicyanoimidazole unit. Tetrahedron Lett 51:2055–2058. doi:10.1016/j.tetlet.2010.02.067

    Article  Google Scholar 

  19. Kulhánek J, Bureš F, Wojciechowski A, Makowska-Janusik M, Gondek E, Kityk VI (2010) Optical operation by chromophores featuring 4,5-dicyanoimidazole embedded within poly(methyl methacrylate) matrices. J Phys Chem A 114:9440–9446. doi:10.1021/jp1047634

    Article  PubMed  Google Scholar 

  20. Nepraš M, Almonasy N, Bureš F, Kulhánek J, Dvořák M, Michl M (2011) Fluorescence and photophysical properties of d-π-a systems featuring a 4,5-dicyanoimidazole unit. Dyes Pigm 91:466–473. doi:10.1016/j.dyepig.2011.03.025

    Article  Google Scholar 

  21. Kulhánek J, Bureš F, Mikysek T, Ludvík J, Pytela O (2011) Imidazole as a central π-linkage in Y-shaped push - pull chromophores. Dyes Pigm 90:48–55. doi:10.1016/j.dyepig.2010.11.004

    Article  Google Scholar 

  22. Kulhánek J, Bureš F, Pytela O, Mikysek T, Ludvík J (2011) Imidazole as a donor/acceptor unit in charge-transfer chromophores with extended π-linkers. Chem Asian J 6:1604–1612. doi:10.1002/asia.201100097

    Article  PubMed  Google Scholar 

  23. Plaquet A, Champagne B, Kulhánek J, Bureš F, Bogdan E, Castet F, Ducasse L, Rodriguez V (2011) Effects of the nature and length of the π-conjugated bridge on the second-order nonlinear optical responses of push-pull molecules including 4,5-dicyanoimidazole and its protonated forms. Chem Phys Chem 12:3245–3252. doi:10.1002/cphc.201100299

    Google Scholar 

  24. Jaing G, Michinobu T, Yuan W, Feng M, Wen Y, Du S, Gao H, Jiang L, Song Y, Diederich F, Zhu D (2005) Crystalline thin fims of s donor-substituted cyanoethene for nanoscale data recording through intramolecular charge-transfer interaction. Adv Mater 17:2170–2173. doi:10.1002/adma.200500559

    Article  Google Scholar 

  25. Haldi A, Kimyonok A, Domercq B, Hayden LE, Jones SC, Marder SR, Weck M, Kippelen B (2008) Optimization of orange-emitting electrophosphorescent copolymers for organic light emitting diodes. Adv Funct Mater 18:3056–3062. doi:10.1002/adfm.200800446

    Article  CAS  Google Scholar 

  26. Innocenzi P, Lebeau B (2005) Organic–inorganic hybrid materials for non-linear optics. J Mater Chem 15:3821–3831. doi:10.1039/b506028a

    Article  CAS  Google Scholar 

  27. Cho MJ, Choi DH, Sullivan PA, Akelaitis APJ, Dalton LR (2008) Recent progress in second non-linear polymer and dendrimers. Prog Polym Sci 33:1013–1058. doi:10.1002/adma.200500559

    Article  CAS  Google Scholar 

  28. Ma H, Lui S, Luo J, Sures S, Lui I, Kang SH, Haller M, Sassa T, Dalton LR, Jen AK-Y (2002) Highly efficient and thermally stable electro-optical polymers and dendrimers. Adv Funct Mater 12:565–574. doi:10.1002/1616-3028(20020916

    Article  CAS  Google Scholar 

  29. Danko M, Hrdlovič P, Kulhánek J, Bureš F (2011) Push-pull fluorophores based on imidazole-4,5-dicarbonitrile: a comparison of spectral properties in solution and in polymer matrices. J Fluores 21:1779–1787. doi:10.1016/j.dyepig.2011.07.011

    Article  CAS  Google Scholar 

  30. Birks JB (1968) Photophysics of Aromatic Molecules. Willey-Interscience a Division of John Wiley and Sons Ltd, New York, London, Toronto, Sidney, Ch 4 pp 121–127

  31. Kawski A, Kubicki A, Kuklinski B, Gryczynski I (1993) Unusual absorption and fluorescence properties of 1,6-diphenyl-1,3,5-hexatriene in poly(vinyl alcohol) film. J Photochem Photobiol A 71:161–167. doi:10.1016/1010-6030(93)85068-J

    Article  CAS  Google Scholar 

  32. Chorvat D Jr, Chorvatova A (2006) Spectrally resolved time-correlated single photon counting: a novel approach for characterization of endogenous fluorescence in isolated cardiac myocytes. Eur Biophys J 36:73–83. doi:10.1007/s00249-006-0104-4

    Article  PubMed  Google Scholar 

  33. Adamson AW, Demas JN (1971) Evaluation of photoluminescence lifetimes. J Phys Chem 57:2463

    Article  Google Scholar 

  34. Demas JN (1973) Excited state lifetime measurements, Appendix E. Academic Press, New York, p 245

    Google Scholar 

  35. Enderlein J, Erdmann R (1997) Fast fitting of multi-exponential decay curves. Opt Commun 134:371–378, (http://www.joerg-enderlein.de/fluo/fluo.html

    Google Scholar 

  36. Morimoto A, Yatsuhashi T, Shimada T, Biczók L, Tryk DA, Inoue H (2001) Radiationless deactivation of intramolecular charge transfer excited state through hydrogen bonding: effect of molecular structure and hard-soft anionic character in the excited state. J Phys Chem A 105:10488–10496. doi:10.1021/jp0117213

    Article  Google Scholar 

  37. Danko M, Kosa C, Andics A, Vegh D, Hrdlovic P (2012) Spectral properties of chalcone containing triphenylamino structural unit in solution and in polymer matrices. Dyes Pigm 92:1257–1265. doi:10.1016/j.dyepig.2011.07.011

    Article  CAS  Google Scholar 

  38. Bangar Raju B, Varadarajan TS (1995) Spectrosopic studies of 7-dimethylamino-3-styryl coumarins. J Photochem Photobiol A 85:263–267. doi:10.1016/1010-6030(94)03905-A

    Article  CAS  Google Scholar 

  39. Hrobarik P, Sigmundova I, Zahradnik P, Kasak P, Arion V, Franz E, Clays K (2010) Molecular engineering of benzothiazolium salt with large quadratic hyperpolarizabilities: can auxiliary electron withdrawing groups enhance nonlinear optical response? J Phys Chem C 114:22289–22302. doi:10.1021/jp108623d

    Article  CAS  Google Scholar 

Download references

Acknowledgement

M. Danko and P. Hrdlovič thank grant agency VEGA for support of project 2/0074/10. This publication is the result of the project implementation: Centre for materials, layers and systems for applications and chemical processes under extreme conditions Stage II supported by the Research & Development Operational Programme funded by the ERDF. J. Kulhánek and F. Bureš thank the Ministry of Education, Youth and Sport of the Czech Republic MSM 0021627501.

Author information

Authors and Affiliations

  1. Polymer Institute, Center of Excellence GLYCOMED, Department of Synthesis and Characterization of Polymers, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41, Bratislava, Slovakia

    Martin Danko

  2. Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 53210, Pardubice, Czech Republic

    Filip Bureš & Jiří Kulhánek

  3. Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41, Bratislava, Slovakia

    Pavol Hrdlovič

Authors
  1. Martin Danko
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Filip Bureš
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiří Kulhánek
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Pavol Hrdlovič
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Martin Danko.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Danko, M., Bureš, F., Kulhánek, J. et al. Spectral Properties of Y-Shaped Donor-Acceptor Push-Pull Imidazole-based Fluorophores: Comparison between Solution and Polymer Matrices. J Fluoresc 22, 1165–1176 (2012). https://doi.org/10.1007/s10895-012-1056-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10895-012-1056-y

Keywords

Search

Navigation