Journal of Fluorescence

, Volume 23, Issue 6, pp 1179–1195 | Cite as

Tuning the Solution Phase Photophysics of Two De Novo Designed Hydrogen Bond Sensitive 9-methyl-2,3,4,9-tetrahydro-1H-carbazol-1-one Derivatives

  • Sujay Ghosh
  • Amrit Krishna Mitra
  • Chandan Saha
  • Samita Basu


Two new fluorophores, 6,7-dimethoxy-9-methyl-2,3,4,9-tetrahydro-1H-carbazol-1-one (DMTCO) and 5-methyl-8,9-dihydro-5H-[1,3]dioxolo[4,5-b]carbazol-6(7H)-one (MDDCO), first of their kind, have been synthesized from the corresponding methoxy and methylenedioxy derivatives of 2,3,4,9-tetrahydro-1H-carbazol-1-one respectively. Comprehensive photophysical characterization of these compounds has been carried out in sixteen different homogeneous solvents and binary solvent mixtures. Both of these compounds are sensitive to solvent polarity, but the sensitivity is much higher in electronic excited state observed by steady-state and time-resolved fluorescence experiments than in ground state studied by UV–vis absorption spectroscopy. The fluorescence spectral shifts are linearly correlated with the empirical parameters of the protic solvents and also the quantitative influence of the empirical solvent parameters on the emission maxima of the compounds has been calculated. The change in dipole moment of the compounds in their excited state has been calculated from the shifts in corresponding emission maxima in pure solvents. A higher dipole moment change of both DMTCO and MDDCO in protic solvents is due to intermolecular hydrogen bonding which is further confirmed by the comparison of their behaviour in toluene-acetonitrile and toluene-methanol solvent mixtures. From structural features, MDDCO is more planar compared to DMTCO, which is reflected better in fluorescence quenching of the former with organic bases, N,N-dimethylaniline and N,N-diethylaniline. Laser flash photolysis experiments prove that the quenching interaction originates from photoinduced electron transfer from the bases to the compounds.


9-methyl-2,3,4,9-tetrahydro-1H-carbazol-1-one Fluorescent probe Lippert-Mataga calculation Hydrogen bond sensitivity Fluorescence quenching Photoinduced electron transfer Laser flash photolysis 



We are thankful to Council of Scientific and Industrial Research (CSIR), New Delhi, India for providing research fellowships to two of the authors [Amrit Krishna Mitra: SRF, File No. 09/951(0003)/2009-EMR-I and Sujay Ghosh: SRF, File No. 09/489(0064)/2009-EMR-I]. This work has been funded by CBAUNP, MMDDA, BARD projects of SINP and DAE, CSIR projects of the Govt. of India. We are also thankful to Prof. Krishnangshu Roy, Director, School of Tropical Medicine, Kolkata and Prof. Milan Kumar Sanyal, Director, Saha Institute of Nuclear Physics, Kolkata for their interest in the work.


  1. 1.
    Lakowicz JR (2006) Principles of Fluorescence Spectroscopy. Springer, New YorkCrossRefGoogle Scholar
  2. 2.
    Ranjith C, Vijayan KK, Praveen VK, Kumar NSS (2010) Photophysical investigation of 3-substituted 4-alkyl and/or 7-acetoxy coumarin derivatives—A study of the effect of substituents on fluorescence. Spectrochim Acta Part A 75:1610–1616CrossRefGoogle Scholar
  3. 3.
    Pişkin M, Durmuş M, Bulut M (2012) Synthesis and investigation on photophysical and photochemical properties of 7-oxy-3-methyl-4-phenylcoumarin bearing zinc phthalocyanines. Spectrochim Acta Part A 97:502–511CrossRefGoogle Scholar
  4. 4.
    Gaber M, El-Daly SA, Fayed TA, El-Sayed YS (2008) Photophysical properties, laser activity and photoreactivity of a heteroaryl chalcone: a model of solvatochromic fluorophore. Opt Las Tech 40:528–537CrossRefGoogle Scholar
  5. 5.
    Bojinov VB, Panova IP, Grabchev IK (2007) Novel polymerizable light emitting dyes – combination of a hindered amine with a 9-phenylxanthene fluorophore. Synthesis and photophysical investigations. Dye Pigm 74:187–194CrossRefGoogle Scholar
  6. 6.
    Feng J, Chen X, Han Q, Wang H, Lu P, Wang Y (2011) Naphthalene-based fluorophores: Synthesis characterization, and photophysical properties. J Lumin 131:2775–2783CrossRefGoogle Scholar
  7. 7.
    Wang ZW, Cao QY, Lin S, Zhuo L, Li ZH (2013) 2,6-Diphenylpyridine-based fluorophores: Synthesis, photophysical properties and effects of protonation. J Photochem Photobiol A 251:106–112CrossRefGoogle Scholar
  8. 8.
    Saito Y, Shinohara Y, Ishioroshi S, Suzuki A, Tanaka M, Saito I (2011) Synthesis of environmentally sensitive 2′-deoxyguanosine containing solvatochromic pyrene fluorophore. Tet Lett 52:2359–2361CrossRefGoogle Scholar
  9. 9.
    Bag SS, Pradhan MK, Kundu R, Jana S (2013) Highly solvatochromic fluorescent naphthalimides: Design, synthesis, photophysical properties and fluorescence switch-on sensing of ct-DNA. BioMed Chem Lett 23:96–101CrossRefGoogle Scholar
  10. 10.
    Ooyama HE, Ooyama Y, Hino T, Sakamoto T, Yamaguchi T, Yoshida K (2011) Synthesis and photophysical properties of structural isomers of novel 2,10-disubstituted benzofuro[2,3-e] naphthoxazole-type fluorescent dyes. Dye Pigm 91:481–488CrossRefGoogle Scholar
  11. 11.
    Firmino ADG, Gonçalves MST (2012) Bifunctionalised long-wavelength fluorescent probes for biological applications. Tet Lett 53:4946–4950CrossRefGoogle Scholar
  12. 12.
    Li Y, Scudiero L, Ren T, Dong WJ (2012) Synthesis and characterizations of benzothiadiazole-based fluorophores as potential wavelength-shifting materials. J Photochem Photobiol A 231:51–59CrossRefGoogle Scholar
  13. 13.
    Dey D, Bose A, Bhattacharyya D, Basu S, Maity SS, Ghosh S (2007) Dibenzo[a, c]phenazine: A Polarity-Insensitive Hydrogen-Bonding Probe. J Phys Chem A 111:10500–10506PubMedCrossRefGoogle Scholar
  14. 14.
    Knölker HJ, Reddy KR (2002) Isolation and synthesis of biologically active carbazole alkaloids. Chem Rev 102:4303–4428PubMedCrossRefGoogle Scholar
  15. 15.
    Schmidt AW, Reddy KR, Knölker HJ (2012) Occurrence, biogenesis, and synthesis of biologically active carbazole alkaloids. Chem Rev 112:3193–3328PubMedCrossRefGoogle Scholar
  16. 16.
    Mitra AK, Ghosh S, Chakraborty S, Sarangi MK, Saha C, Basu S (2012) Photophysical properties of an environment sensitive fluorophore 1-keto-6,7-dimethoxy-1,2,3,4-tetrahydrocarbazole and its excited state interaction with N, N-dimethylaniline: A spectroscopic investigation. J Photochem Photobiol A 240:66–74CrossRefGoogle Scholar
  17. 17.
    Chakraborty S, Chattopadhyay G, Saha C (2011) Montmorillonite-KSF induced Fischer indole cyclization under microwave towards a facile entry to 1-keto-1,2,3,4-tetrahydrocarbazoles. Ind J Chem B 50:201–206Google Scholar
  18. 18.
    Mitra AK, Ghosh S, Chakraborty S, Basu S, Saha C Synthesis and Spectroscopic Exploration of Carboxylic Acid Derivatives of 6-Hydroxy-1-Keto-1,2,3,4-tetrahydrocarbazole: Hydrogen Bond Sensitive Fluorescent Probes. J Lumin acceptedGoogle Scholar
  19. 19.
    Kawski A, Bojarski P, Kuklinski B (2008) Estimation of ground-and excited-state dipole moments of Nile red dye from solvatochromic effect on absorption and fluorescence spectra. Chem Phys Lett 463:410–412CrossRefGoogle Scholar
  20. 20.
    Lippert E (1957) Spektroskopische bestimmung des dipolmomentes aromatischer Verbindungen im ersten angeregten singulettzustand. Ber Bunsenges Phys Chem 61:962–975Google Scholar
  21. 21.
    Mataga N, Kaifu Y, Koizumi M (1956) Solvent effects upon fluorescence spectra and the dipolemoments of excited molecules. Bull Chem Soc Jpn 29:465–470CrossRefGoogle Scholar
  22. 22.
    Kamlet MJ, Abboud JLM, Abraham MH, Taft RW (1983) Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, pi.*, alpha., and.beta., and some methods for simplifying the generalized solvatochromic equation. J Org Chem 48:2877–2887CrossRefGoogle Scholar
  23. 23.
    Abraham MH, Grellier PL, Abboud JLM, Doherty RM, Taft RW, Doherty M (1988) Solvent effects in organic chemistry — recent developments. Can J Chem 66:2673–2686CrossRefGoogle Scholar
  24. 24.
    Kamlet MJ, Abboud JLM, Taft RW (1977) The solvatochromic comparison method. 6. The.pi.* scale of solvent polarities. J Am Chem Soc 99:6027–6038CrossRefGoogle Scholar
  25. 25.
    Kamlet MJ, Taft RW (1976) The solvatochromic comparison method. I. The.beta.-scale of solvent hydrogen-bond acceptor (HBA) basicities. J Am Chem Soc 98:377–383CrossRefGoogle Scholar
  26. 26.
    Taft RW, Abboud JLM, Kamlet MJ (1981) Solvatochromic comparison method. 20. Linear solvation energy relationships. 12. The term in the solvatochromic equations. J Am Chem Soc 103:1080–1086CrossRefGoogle Scholar
  27. 27.
    Taft RW, Kamlet MJ (1976) The solvatochromic comparison method. 2. The.alpha.-scale of solvent hydrogen-bond donor (HBD) acidities. J Am Chem Soc 98:2886–2894CrossRefGoogle Scholar
  28. 28.
    Kamlet MJ, Dickinson C, Taft RW (1981) Linear solvation energy relationships Solvent effects on some fluorescence probes. Chem Phys Lett 77:69–72CrossRefGoogle Scholar
  29. 29.
    Critchfield FE, Gibson JA, Hall JL (1953) Dielectric constant for the dioxane—water system from 20 to 35°. J Am Chem Soc 75:1991–1992CrossRefGoogle Scholar
  30. 30.
    Geddes JA (1933) The fluidity of dioxane - water mixtures. J Am Chem Soc 55:4832–4837CrossRefGoogle Scholar
  31. 31.
    Stallard RD, Amis ES (1952) Heat of vaporization and other properties of dioxane, water and their mixtures. J Am Chem Soc 74:1781–1790CrossRefGoogle Scholar
  32. 32.
    Kosower EM, Dodiuk H, Tanizawa K, Ottolenghi M, Orbach N (1975) Intramolecular donor - acceptor systems. Radiative and nonradiative processes for the excited states of 2-N-arylamino-6-naphthalenesulfonates. J Am Chem Soc 97:2167–2178CrossRefGoogle Scholar
  33. 33.
    Reynolds L, Gardecki JA, Frankland SJV, Horng ML, Maroncelli M (1996) Dipole Solvation in nondipolar solvents: experimental studies of reorganization energies and solvation dynamics. J Phys Chem 100:10337–10354CrossRefGoogle Scholar
  34. 34.
    Suppan P (1990) Invited review solvatochromic shifts: the influence of the medium on the energy of electronic states. J Photochem Photobiol A 50:293–330CrossRefGoogle Scholar
  35. 35.
    Kro´licki R, Jarzeba W, Mostafavi M, Lampre I (2002) J Phys Chem A 106:1708–1713CrossRefGoogle Scholar
  36. 36.
    Tang R, Zhang P, Lia H, Liu Y, Wang W (2011) Photosensitized xanthone-based oxidation of guanine and its repair: a laser flash photolysis study. J Photochem Photobiol B 105:157–161PubMedCrossRefGoogle Scholar
  37. 37.
    Li K, Wang H, Cheng L, Wang M, Zhua R, Wang SL (2011) Characterization of transient species produced from laser flash photolysis of a new cardioprotective drug: S-propargyl-cysteine. J Photochem Photobiol B 219:195–199CrossRefGoogle Scholar
  38. 38.
    Rigoli IC, Bonilha JBS, Quina FH, Okano LT, Naal RMZG (2011) Photoreactions of n-alkyl-3-nitrophenyl ethers with aromatic amines in SDS micelles: a laser flash photolysis study. J Photochem Photobiol A 222:34–39CrossRefGoogle Scholar
  39. 39.
    Sarangi MK, Basu S (2011) Associated electron and proton transfer between Acridine and Triethylamine in AOT reverse micelles probed by laser flash photolysis with magnetic field. Chem Phys Lett 506:205–210CrossRefGoogle Scholar
  40. 40.
    Wang JT, Sun Q, Zhang LM, Yu SQ (2010) Solvent effects of photoinduced electron transfer reactions of triplet fluorenone with amines. Chin Sci Bull 55:2891–2895CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Sujay Ghosh
    • 1
  • Amrit Krishna Mitra
    • 2
  • Chandan Saha
    • 2
  • Samita Basu
    • 1
  1. 1.Chemical Sciences DivisionSaha Institute of Nuclear PhysicsKolkataIndia
  2. 2.Department of Clinical and Experimental Pharmacology, School of Tropical MedicineKolkataIndia

Personalised recommendations