Skip to main content
SpringerLink
Log in

Photoinduced intramolecular charge transfer in trans-2-[4′-(N, N-dimethylamino)styryl]imidazo[4,5- b]pyridine: effect of introducing a C=C double bond

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

The spectral characteristics of trans-2-[4′-(N, N-dimethylamino)styryl]imidazo[4,5- b]pyridine (t-DMASIP-b) have been investigated using absorption and fluorescence techniques, and compared with 2-(4′- N, N-dimethylamino)imidazo[4,5- b]pyridine (DMAPIP-b). The study reveals that introduction of a C=C double bond strongly perturbs the photophysics of the system. Unlike DMAPIP-b, t-DMASIP-b emits a single emission in aprotic and protic solvents. The emission occurs from the locally excited state in nonpolar solvents and from a planar intramolecular charge transfer (PICT) state in polar solvents. Multiple linear regression analysis suggests that among the different solvent parameters, the dipolar interaction contributes more to the stabilization of the system in both the ground and excited states. Theoretical calculations suggest that, unlike in DMAPIP-b, proton coupled twisted intramolecular charge transfer (TICT) emission does not occur in t-DMASIP-b. The higher quantum yield obtained in the viscous solvent glycerol is attributed to the restriction of the twisting of the olefinic bond. The photoirradiation of t-DMASIP-b shows that isomerization takes place in all solvents, including viscous glycerol. The theoretically simulated potential energy surface shows that isomerization occurs via a phantom state, which is a nonradiative process. The rise in temperature favors the photoisomerization, thus, the fluorescence quantum yield decreases. The prototropic study indicates that, unlike in DMAPIP-b, the protonation takes place at different places to form the monocations.

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

Similar content being viewed by others

References

  1. W. Rettig, Charge separation in excited states of decoupled systems-TICT compounds and implications regarding the development of new laser dyes and the primary process of vision and Photosynthesis, Angew. Chem., Int. Ed. Engl., 1986, 25, 971–988.

    Article  Google Scholar 

  2. J. Stubbe, D. G. Nocera, C. S. Yee, M. C. Y. Chang, Radical initiation in the class I ribonucleotide reductase: long-range proton-coupled electron transfer?, Chem. Rev., 2003, 103, 2202.

    Article  CAS  Google Scholar 

  3. S. Y. Reece, D. G. Nocera, Proton-coupled Electron Transfer in Biology: results from synergistic studies in natural and model systems, Annu. Rev. Biochem., 2009, 78, 673–699.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. S. Hammes-Schiffer, A. V. Soudackov, Proton-coupled electron transfer in solution, proteins, and electrochemistry, J. Phys. Chem. B, 2008, 112, 14108–14123.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. S. Perrier, E. Mugeniwabagara, A. Kirsch-De Mesmaeker, P. J. Hore, M. Luhmer, Exploring photoreactions between polyazaaromatic Ru(II) complexes and Biomolecules by chemically induced dynamic nuclear polarization measurements, J. Am. Chem. Soc., 2009, 131, 12458–12465.

    Article  CAS  PubMed  Google Scholar 

  6. Y. Tachibana, S. Makuta, Y. Otsuka, J. Terao, S. Tsuda, N. Kambe, S. Seki, S. Kuwabata, Organic conducting wire formation on a TiO2 nanocrystalline structure: towards long-lived charge separated systems, Chem. Commun., 2009, 4360–4362.

    Google Scholar 

  7. Z. R. Grabowski, K. Rotkiewicz, W. Rettig, Structural changes accompanying intramolecular electron transfer: focus on twisted intramolecular charge-transfer states and structures, Chem. Rev., 2003, 103, 3899–4031.

    Article  PubMed  Google Scholar 

  8. J. Dobkowski, J. Wojcik, W. Kozminski, R. Kołs, J. Waluk, J. Michl, An experimental test of C-N bond twisting in the TICT state: syn-anti photoisomerization in 2-(N-Methyl-N-isopropylamino)-5-cyanopyridine, J. Am. Chem. Soc., 2002, 124, 2406–2407.

    Article  CAS  PubMed  Google Scholar 

  9. T. Yoshihara, S. I. Druzhinin, K. A. Zachariasse, Fast intramolecular charge transfer with a planar rigidized electron donor/acceptor molecule, J. Am. Chem. Soc., 2004, 126, 8535–8539.

    Article  CAS  PubMed  Google Scholar 

  10. K. A. Zachariasse, S. I. Druzhinin, W. Bosch, R. Machinek, Intramolecular charge transfer with the planarized 4-aminobenzonitrile 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6), J. Am. Chem. Soc., 2004, 126, 1705–1715.

    Article  CAS  PubMed  Google Scholar 

  11. K. Rotkiewicz, K. H. Grellmann, Z. R. Grabowski, Reinterpretation of the anomalous fluorescence of p-n,n-dimethylamino-benzonitrile, Chem. Phys. Lett., 1973, 19, 315–318.

    Article  CAS  Google Scholar 

  12. S. I. Druzhinin, S. A. Kovalenko, T. A. Senyushkina, A. Demeter, R. Januskevicius, P. Mayer, D. Stalke, R. Machinek, K. A. Zachariasse, Intramolecular charge transfer with 4-fluorofluorazene and the flexible 4-fluoro-N-phenylpyrrole, J. Phys. Chem., 2009, 113, 9304–9320.

    Article  CAS  Google Scholar 

  13. S. Cogan, S. Zilberg, Y. Haas, The electronic origin of the dual fluorescence in donor-acceptor substituted benzene derivatives, J. Am. Chem. Soc., 2006, 128, 3335–3345.

    Article  CAS  PubMed  Google Scholar 

  14. M. Dekhtyar, W. Rettig, Charge-transfer transitions in twisted stilbenoids: interchangeable features and generic distinctions of single- and double-bond twists, J. Phys. Chem. A, 2007, 111, 2035–2039.

    Article  CAS  PubMed  Google Scholar 

  15. R. Lapouyade, A. Kuhn, J.-F. Letard, W. Rettig, Multiple relaxation pathways in photoexcited dimethylaminonitro- and dimethylaminocyano-stilbenes, Chem. Phys. Lett., 1993, 208, 48–58.

    Article  CAS  Google Scholar 

  16. V. Papper, D. Pines, G. Likhtenshtein, E. Pines, Photophysical characterization of trans-4,4′-disubstituted stilbenes, J. Photochem. Photobiol., A, 1997, 111, 87–96.

    Article  CAS  Google Scholar 

  17. M. L. Christophe, V. Velde, F. Blockhuys, C. V. Alsenoy, A. T. H. Lenstra, H. J. Geise, Structural effects influencing cis-transisomerisation in methoxy and cyano substituted stilbene derivatives, J. Chem. Soc., Perkin Trans. 2, 2002, 1345–1351.

    Google Scholar 

  18. H. Le Breton, B. Bennetau, J.-F. Letard, I. R. Lapouyade, W. Rettig, Nonradiative twisted intramolecular charge transfer state in polar stilbenes: photophysical study of 4-pedtuorooctylsulfonyl-4′-N,N-dimethylamino stilbene and two bridged derivatives, J. Photochem. Photobiol., A, 1996, 95, 7–20.

    Article  Google Scholar 

  19. M. Shaikh, J. Mohanty, P. K. Singh, A. C. Bhasikuttan, R. N. Rajule, V. S. Satam, S. R. Bendre, V. R. Kanetkar, H. Pal, Contrasting solvent polarity effect on the photophysical properties of two newly synthesized aminostyryl dyes in the lower and in the higher solvent polarity regions, J. Phys. Chem. A, 2010, 114, 4507–4519.

    Article  CAS  PubMed  Google Scholar 

  20. W. Akemann, D. Laage, P. Plaza, M. M. Martin, M. Blanchard-Desce, Photoinduced intramolecular charge transfer in push-pull polyenes: effects of solvation, electron-donor group, and polyenic chain length, J. Phys. Chem. B, 2008, 112, 358–368.

    Article  CAS  PubMed  Google Scholar 

  21. D. Seth, S. Sarkar, R. Pramanik, C. Ghatak, P. Setua, N. Sarkar, Photophysical studies of a hemicyanine dye (LDS-698) in dioxane-water mixture, in different alcohols, and in a room temperature ionic liquid, J. Phys. Chem. B, 2009, 113, 6826–6833.

    Article  CAS  PubMed  Google Scholar 

  22. S. E.-D. H. Etaiw, T. A. Fayed, N. Z. Saleh, Photophysics of benzazole derived push-pull butadienes: a highly sensitive fluorescence probes, J. Photochem. Photobiol., A, 2006, 177, 238–247.

    Article  CAS  Google Scholar 

  23. X.-M. Wang, Y.-F. Zhou, W.-T. Yu, C. Wang, Q. Fang, M.-H. Jiang, H. Lei, H.-Z. Wang, Two-photon pumped lasing stilbene-type chromophores containing various terminal donor groups: relationship between lasing efficiency and intramolecular charge transfer, J. Mater. Chem., 2000, 10, 2698–2703.

    Article  CAS  Google Scholar 

  24. C. Qin, W. Zhang, Z. Wang, M. Zhou, X. Wang, G. Chen, Optical properties of stilbene-type dyes containing various terminal donor and acceptor groups, Opt. Mater., 2008, 30, 1607–1615.

    Article  CAS  Google Scholar 

  25. R. J. Clarke, H.-J. Apell, B. Y. Kong, Allosteric effect of ATP on Na+,K+-ATPase conformational kinetics, Biochemistry, 2007, 46, 7034–7044.

    Article  CAS  PubMed  Google Scholar 

  26. L. Moreaux, T. Pons, V. Dambrin, M. Blanchard-Desce, J. Mertz, Electro-optic response of second-harmonic generation membrane potential sensors, Opt. Lett., 2003, 28, 625–627.

    Article  CAS  PubMed  Google Scholar 

  27. D. A. Dombeck, L. Sacconi, M. Blanchard-Desce, W. W. Webb, Optical recording of fast neuronal membrane potential transients in acute mammalian brain slices by second-harmonic generation microscopy, J. Neurophysiol., 2005, 94, 3628–3636.

    Article  PubMed  Google Scholar 

  28. S. Arzhantsev, K. A. Zachariasse, M. Maroncelli, Photophysics of trans-4-(dimethylamino)-4′-cyanostilbene and its use as a solvation probe, J. Phys. Chem., 2006, 110, 3454–3470.

    Article  CAS  Google Scholar 

  29. J.-S. Yang, K.-L. Liau, C.-M. Wang, C.-Y. Hwang, Substituent-dependent photoinduced intramolecular charge transfer in N-aryl-substituted trans-4-aminostilbenes, J. Am. Chem. Soc., 2004, 126, 12325–12335.

    Article  CAS  PubMed  Google Scholar 

  30. J.-S. Yang, C.-K. Lin, A. M. Lahoti, C.-K. Tseng, Y.-H. Liu, G.-H. Lee, S.-M. Peng, Effect of ground-state twisting on the trans → cis photoisomerization and TICT state formation of aminostilbenes, J. Phys. Chem. A, 2009, 113, 4868–4877.

    Article  CAS  PubMed  Google Scholar 

  31. S. S. Quintana, F. Moyano, R. Darío Falcone, J. J. Silber, N. Mariano Correa, Characterization of Multifunctional Reverse Micelles’ Interfaces Using Hemicyanines as Molecular Probes. II: Effect of the Surfactant, J. Phys. Chem. B, 2009, 113, 6718–6724.

    Article  CAS  PubMed  Google Scholar 

  32. C. A. van Walree, B. C. van der Wiel, R. M. Williams, Photoinduced charge transport over branched conjugation pathways: donor-acceptor substituted 1,1-diphenylethene and 2,3-diphenylbutadiene, Phys. Chem. Chem. Phys., 2013, 15, 15234–15242.

    Article  PubMed  CAS  Google Scholar 

  33. B. C. van der Wiel, R. M. Williams, C. A. van Walree, Photoinduced charge separation in a donor-acceptor functionalized 2,3-diphenylbutadiene: charge transport over a doubly bifurcated π-spacer, Org. Biomol. Chem., 2004, 2, 3432–3433.

    Article  PubMed  Google Scholar 

  34. M. Quintiliani, A. Kahnt, T. Wölfle, W. Hieringer, P. Vázquez, A. Görling, D. M. Guldi, T. Torres, Synthesis and Photoinduced Electron Transfer Properties of Phthalocyanine-[60]Fullerene Conjugates, Chem. - Eur. J., 2008, 14, 3765–3775.

    Article  CAS  PubMed  Google Scholar 

  35. V. Bavetsias, C. Sun, N. Bouloc, J. Reynisson, P. Workman, S. Linardopoulos, M. Edward, Hit generation and exploration: imidazo[4,5-b]pyridine derivatives as inhibitors of Aurora kinases, Bioorg. Med. Chem. Lett., 2007, 17, 6567–6571.

    Article  CAS  PubMed  Google Scholar 

  36. N. Dash, F. A. S. Chipem, R. Swaminathan, G. Krishnamoorthy, Hydrogen bond induced twisted intramolecular charge transfer in 2-(4′-N,N-dimethylaminophenyl)imidazo[4,5-b]pyridine, Chem. Phys. Lett., 2008, 460, 119–124.

    Article  CAS  Google Scholar 

  37. A. Mishra, G. Krishnamoorthy, Photophysical study of 2-(4′- N, N-dimethylaminophenyl)oxazolo[4,5- b]pyridine in different solvents and at various pH, Photochem. Photobiol. Sci., 2012, 11, 1356–1367.

    Article  CAS  PubMed  Google Scholar 

  38. A. Mishra, S. Sahu, N. Dash, S. K. Behera, G. Krishnamoorthy, Double proton transfer induced twisted intramolecular charge transfer emission in 2-(4′- N, N-dimethylaminophenyl)imidazo[4,5-b]pyridine, J. Phys. Chem. B, 2013, 117, 9469–9477.

    Article  CAS  PubMed  Google Scholar 

  39. Organic molecules for nonlinear optics and photonics, ed. J. Messier, F. Kajzar and P. Prasad, Kluwer Academic Publishers, Dordrecht, Boston, 1991.

    Google Scholar 

  40. Z. S. Wang, F. Y. Li, C. H. Huang, L. Wang, M. Wei, L. P. Jin, N. Q. Li, Photoelectric conversion properties of nanocrystalline TiO2 electrodes sensitized with hemicyanine derivatives, J. Phys. Chem. B, 2000, 104, 9676–9682.

    Article  CAS  Google Scholar 

  41. S. K. Dogra, Intra and intermolecular proton transfer reactions of 2-Phenyl substituted benzazoles, Proc. Indian Acad. Sci., 1992, 104, 635–647.

    CAS  Google Scholar 

  42. E. Lippert, Spektroskopische bistimmung des dipolmomentes aromatischer verbindugen im ersten angeregten singulettzustand, Z. Elektrochem., 1957, 61, 962–975.

    CAS  Google Scholar 

  43. M. H. Abraham, P. L. Greillier, J. L. M. Abboud, R. M. Doherty, R. W. Taft, Effects in organic chemistry - recent developments, Can. J. Chem., 1988, 66, 2673–2686.

    Article  CAS  Google Scholar 

  44. M. J. Kamlet, J. L. M. Abboud, M. H. Abraham, R. W. Taft, Linear Solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, π*, α, and β, and some methods for simplifying the generalized solvatochromic equation, J. Org. Chem., 1983, 48, 2877–2887.

    Article  CAS  Google Scholar 

  45. K. Rotkiewicz, K. H. Grellmann, Z. R. Grabowski, Reinterpretation of the anomalous fluorescence of p-n,n-dimethylamino-benzonitrile, Chem. Phys. Lett., 1973, 19, 315–318.

    Article  CAS  Google Scholar 

  46. S. I. Druzhinin, S. A. Kovalenko, T. A. Senyushkina, A. Demeter, R. Januskevicius, P. Mayer, D. Stalke, R. Machinek, K. A. Zachariasse, Intramolecular charge transfers with 4-fluorofluorazene and the flexible 4-fluoro-N-phenylpyrrole, J. Phys. Chem. A, 2009, 113, 9304–9320.

    Article  CAS  PubMed  Google Scholar 

  47. T. A. Fayed, Intramolecular Charge transfer and photoisomerization of 2-(p-Dimethylaminostyryl)benzoxazole: - a new fluorescent probe, J. Photochem. Photobiol., A, 1999, 121, 17–25.

    Article  CAS  Google Scholar 

  48. S. K. Saha, P. Purkayastha, A. B. Das, S. Dhara, Excited state isomerization and effect of viscosity and temperature-dependent torsional relaxation on TICT fluorescence of trans-2-[4-(dimethylamino)styryl]benzothiazole, J. Photochem. Photobiol., A, 2008, 199, 179–187.

    Article  CAS  Google Scholar 

  49. J. Saltiel, Y.-P. Sun, The intrinsic potential energy barrier for twisting in the trans-stilbene S1 state in hydrocarbon solvents, J. Phys. Chem., 1989, 93, 6246–6250.

    Article  CAS  Google Scholar 

  50. A. Mishra, A. Thangamni, S. Chatterjee, F. A. S. Chipem, G. Krishnamoorthy, Photoisomerization of trans-2-[4′-(Dimethylamino)Styryl]benzothiazole, Photochem. Photobiol., 2013, 39, 247–252.

    Article  CAS  Google Scholar 

  51. D. H. Waldeck, Photoisomerization Dynamics of stilbenes, Chem. Rev., 1991, 91, 415–436.

    Article  CAS  Google Scholar 

  52. J. Saltiel, J. T. D. Agostino, Separation of viscosity and temperature effects on the singlet pathway to stilbene photoisomerization, J. Am. Chem. Soc., 1972, 94, 6445–6456.

    Article  CAS  Google Scholar 

  53. S. Malkin, E. Fischer, Temperature dependence of photoisomerization. III. Direct and sensitized photoisomerization of stilbenes, J. Phys. Chem., 1964, 68, 1153–1163.

    Article  CAS  Google Scholar 

  54. J. Saltiel, A. S. Waller, D. F. Sears Jr., E. A. Hoburg, D. M. Zeglinski, D. H. Waldeck, Fluorescence quantum yields and lifetimes of substituted stilbenes in n-Alkanes. A reexamination of the relationship between solute size and medium effect on torsional relaxation, J. Phys. Chem., 1994, 98, 10689–10698.

    Article  CAS  Google Scholar 

  55. J. Saltiel, A. Waller, Y.-P. Sun, D. F. Sears Jr., Cis-stilbene fluorescence in solution. adiabatic c* to t* conversion, J. Am. Chem. Soc., 1990, 112, 4580–4581.

    Article  CAS  Google Scholar 

  56. J. Saltiel, A. S. Waller, D. F. Sears Jr., Dynamics of cis stilbene photoisomerization: The adiabatic pathway to excited trans stilbene, J. Photochem. Photobiol., A, 1992, 65, 29–40.

    Article  CAS  Google Scholar 

  57. J. Saltiel, A. S. Waller, D. F. Sears Jr., The temperature and medium dependencies of cis-stilbene fluorescence. The energetics for twisting in the lowest excited singlet state, J. Am. Chem. Soc., 1993, 115, 2453–2465.

    Article  CAS  Google Scholar 

  58. S. Sharafy, K. A. Muszka, Viscosity dependence of fluorescence quantum Yields, J. Am. Chem. Soc., 1971, 93, 4119–4125.

    Article  CAS  Google Scholar 

  59. C. Dugave, L. Demange, Cis-trans isomerization of organic molecules and biomolecules: implications and applications, Chem. Rev., 2003, 103, 2475–2532.

    Article  CAS  PubMed  Google Scholar 

  60. I. Gryczyński, A. Kawski, Temperaturabhängigkeit der statischen dielektrizitätskonstante und des optischen brechungsindexes von flüssigkeiten, Z. Naturforsch., 1975, 30a, 287–293.

    Article  Google Scholar 

  61. N. Dash, F. A. S. Chipem, G. Krishnamoorthy, Encapsulation of 2-(4′-N,N-Dimethylaminophenyl)imidazo[4,5-b]pyridine in β-cyclodextrin: effect on H-bond-induced intramolecular charge transfer emission, Photochem. Photobiol. Sci., 2009, 8, 1708–1715.

    Article  CAS  PubMed  Google Scholar 

  62. N. Dash, G. Krishnamoorthy, Photophysics of 2-(4′-N,N-dimethylaminophenyl)imidazo[4,5-b]pyridine in micelles: selective dual fluorescence in sodium dodecyl sulphate and triton X-100, J. Fluoresc., 2010, 20, 135–142.

    Article  CAS  PubMed  Google Scholar 

  63. G. Krishnamoorthy, S. K. Dogra, Spectral characteristics of various prototropic species of 2-(4′- N, N-dimethylaminophenyl)pyrido[3,4-d]imidazole, J. Org. Chem., 1999, 64, 6566–6574.

    Article  CAS  PubMed  Google Scholar 

  64. J. K. Dey, S. K. Dogra, Dual fluorescence of 2-(4′-N,N-(Dimethylamino)phenyl)benzothiazole and its benzimidazole analogue: effects of solvents and pH on electronic spectra, J. Phys. Chem., 1994, 98, 3638–3644.

    Article  CAS  Google Scholar 

  65. C. J. Drummond, F. Grieser, T. W. Healy, Interfacial properties of a novel group of solvatochromic acid-base indicators in self-assembled surfactant aggregates, J. Phys. Chem., 1988, 92, 2604–2613.

    Article  CAS  Google Scholar 

  66. C. J. Drummond, F. Grieser, T. W. Healy, Acid-base equilibria in aqueous micellar solutions. Part 1, J. Chem. Soc., Faraday, Trans. 1, 1988, 85, 521–535.

    Article  Google Scholar 

  67. A. K. Mishra, S. K. Dogra, Effects of solvent and pH on the absorption and fluorescence spectra of 2-Phenylbenzimidazole, Spectrochim. Acta, Part A, 1983, 39, 609–611.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Guwahati, 781039, India

    Anasuya Mishra, Saugata Sahu, Shreya Tripathi & G. Krishnamoorthy

Authors
  1. Anasuya Mishra
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Saugata Sahu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Shreya Tripathi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. G. Krishnamoorthy
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to G. Krishnamoorthy.

Additional information

† Electronic supplementary information (ESI) available: Details of materials and methods, absorption spectra in different solvents, Lippert-Mataga equation, plot of temperature dependence of fluorescence quantum yield and emission spectra at different pHs. See DOI: 10.1039/c4pp00237g

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mishra, A., Sahu, S., Tripathi, S. et al. Photoinduced intramolecular charge transfer in trans-2-[4′-(N, N-dimethylamino)styryl]imidazo[4,5- b]pyridine: effect of introducing a C=C double bond. Photochem Photobiol Sci 13, 1476–1486 (2014). https://doi.org/10.1039/c4pp00237g

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c4pp00237g

Search

Navigation