Journal of Fluorescence

, Volume 21, Issue 1, pp 65–80 | Cite as

Synthesis and Photophysics of Some Novel Imidazole Derivatives Used as Sensitive Fluorescent Chemisensors

  • Kanagarathinam Saravanan
  • Natesan Srinivasan
  • Venugopal Thanikachalam
  • Jayaraman Jayabharathi
Original Paper


Some novel imidazole derivatives were developed for highly sensitive chemisensors for transition metal ions. Since these compounds are sensitive to different external stimulations such as UV irradiation, heat, increasing pressure and changing the environmental pH causing colour change and so they can be used as a ′multi-way′ optically switchable material. A prominent fluorescence enhancement was found in the presence of transition metal ions such as Hg2+, Pb2+ and Cu2+ and this was suggested to result from the suppression of radiationless transitions from the n-π* state in the chemisensors. The existence of C-H….O intramolecular hydrogen bonding in dmphnpi is confirmed by the Natural Bond Orbital analysis (NBO). The Mulliken, NBO charge analysis and the HOMO-LUMO energies were also calculated. The electric dipole moment (μ) and the first-hyperpolarisability (β) value of the investigated molecules have been studied both experimentally and theoretically which reveal that the synthesized molecules have microscopic non-linear optical (NLO) behaviour with non-zero values. Ground and excited state DFT calculation were carried out in order to find out dipole moment and energy.


NMR Emission kinetics Chemisensors NLO HOMO-LUMO 



One of the author Dr. J. Jayabharathi, Reader in Chemistry, Annamalai University is thankful to Department of Science and Technology [No. SR/S1/IC-07/2007], University Grants commission (F. No. 36-21/2008 (SR)) for providing fund to this research work.


  1. 1.
    Santos J, Mintz EA, Zehnder O, Bosshard C, Bu XR, Gunter P (2001) New class of imidazoles incorporated with thiophenvinyl conjugation pathway for robust nonlinear optical chromophores. Tetrahedron Lett 42:805–808CrossRefGoogle Scholar
  2. 2.
    Huang WS, Lin JT, Chien CH, Tao YT, Sun SS, Wen YS (2004) Highly phosphorescent Bis-cyclometalated Iridium complexes containing Benzimidazole-Based ligands. Chem Mater 16:2480–2488CrossRefGoogle Scholar
  3. 3.
    Chen CH, Shi J (1998) Metal chelates as emitting materials for organic electroluminescence. Coord Chem Rev 171:161–174Google Scholar
  4. 4.
    Kamidate T, Yamaguchi K, Segawa T (1989) Lophine Chemiluminescence for Determination of Chromium(VI) by Continuous Flow Method H. Watanabe. Anal Sci 5:429–433CrossRefGoogle Scholar
  5. 5.
    Nakashima K, Yamasaki H, Kuroda N, Akiyama S (1995a) Evaluation of lophine derivatives as chemiluminogens by a flow injection method. Anal Chim Acta 303:103–107CrossRefGoogle Scholar
  6. 6.
    Nakashima K (2003b) Lophine derivatives as versatile analytical tools. Biomed Chromatogr 17:83–95CrossRefGoogle Scholar
  7. 7.
    MacDonald A, Chain KW, Nieman TA (1979) Lophine chemluminescence for metal ion determinations. Anal Chem 51:2077–2082CrossRefGoogle Scholar
  8. 8.
    Marino DF, Ingle JD Jr (1981) Determination of Chromium(VI) in water by lophine chemiluminescence. Anal Chem 53:294–298CrossRefGoogle Scholar
  9. 9.
    Lipshutz BH (1986) Five-membered hetero aromatic rings as intermediates in organic synthesis. Chem Rev 86:795–819CrossRefGoogle Scholar
  10. 10.
    Ucucu U, Karaburun NG, Isikdag I (2001) Synthesis and analgesic activity of some 1-benzyl-2-substituted-4, 5-diphenyl-1H-imidazole derivatives. I L Farmaco 56:285–290Google Scholar
  11. 11.
    Nakashima K, Taguchi Y, Kuroda N, Akiyama S, Duan G (1993) 2-(4-Hydrazinocarbonylphenyl)-4, 5-diphenylimidazole as a versatile fluorescent derivatization reagent for the high-performance liquid chromatographic analysis of free fatty acids. J Chromatogr 619:1–8CrossRefPubMedGoogle Scholar
  12. 12.
    Yagi K, Soong CF, Irie M (2001) Synthesis of fluorescentdiarylethenes having a 2, 4, 5-triphenylimidazole chromophore. J Org Chem 66:5419–5423CrossRefPubMedGoogle Scholar
  13. 13.
    Gostev FE, Kol’tsova LS, Petrukhin AN, Titov AA, Shiyonok AI, Zaichenko NL, Marevtsev VS, Sarkisov M (2003) Spectral luminescence properties and dynamics of intramolecular processes in 2,4,5-triarylimidazoles. J Photochem Photobiol A 156:15–22CrossRefGoogle Scholar
  14. 14.
    Feng K, Hsu F-L, Veer DVD, Bota K, Bu XR (2004) Tuning fluorescence properties of imidazole derivatives with thiophene and thiozole. J Photochem Photobiol A 165:223–228CrossRefGoogle Scholar
  15. 15.
    Hennessy J, Testa AC (1972) Photochemistry of phenylimidazoles. J Phys Chem 76:3362–3365CrossRefGoogle Scholar
  16. 16.
    Guassian 03 program, (Gaussian Inc., Wallingford CT) 2004Google Scholar
  17. 17.
    Schlegel HB (1982) Optimization of equilibrium geometries and transition structures. J Comput Chem 3:214–218CrossRefGoogle Scholar
  18. 18.
    Jayabharathi J, Thanikachalam V, Saravanan K (2009) Effect of substituents on the photoluminescence performance of Ir(III) complexes: Synthesis, electrochemistry and photophysical properties. J Photochem Photobiol A 208:13–20CrossRefGoogle Scholar
  19. 19.
    Ren P, Liu T, Qin J, Chen C (2003) A new approach to suppress nonlinearity-transparency trade-off through coordination chemistry: syntheses and spectroscopic study on second-order nonlinear optical properties of a series of square-pyramidal zinc(II) complexes. Spectrochim Acta A 59:1095–1101CrossRefGoogle Scholar
  20. 20.
    Fridmam N, Kaftory M, Speiser S (2007) Structures and photophysics of lophine and double lophine derivatives. Sens Actuators B 126:107–115CrossRefGoogle Scholar
  21. 21.
    Balamurali MM, Dogra SK (2004) Intra- and Intermolecular proton transfer in methyl-2-hydroxynicotinate. J Luminescence 110:147–163Google Scholar
  22. 22.
    Mazumdar S, Manoharan R, Dogra SK (1989) Solvatochromic effects in the fluorescence of a few diamino aromatic compounds. J Photochem Photobiol A 46:301–314CrossRefGoogle Scholar
  23. 23.
    Zhou Z, Fahrni CJ (2004) A fluorogenic probe for the copper(I)-catalyzed azide-alkyne ligation reaction: modulation of the fluorescence emission via 3(n,π*)-1(π, π*) inversion. J Am Chem Soc 126:8862–8863CrossRefPubMedGoogle Scholar
  24. 24.
    Weiss MS, Brandl M, Suhnel J, Pal D, Hilgenfeld R (2001) More hydrogen bonds for the (structural) biologist. Trends Biochem Sci 26:521–523CrossRefPubMedGoogle Scholar
  25. 25.
    Riebeiro-Claro PJA, Drew MGB, Felix V (2002) C-H….O bonded dimers in 2-methoxy-benzaldehyde studied by X-ray crystallography, Vibrational spectroscopy, and ab initio calculations. Chem Phys Lett 356:318–324CrossRefGoogle Scholar
  26. 26.
    Hermansson K (2002) Blue-shifting Hydrogen bonds. J Phys Chem A 106:4695–4702CrossRefGoogle Scholar
  27. 27.
    Sato H, Dybal J, Murakami R, Noda I, Ozaki Y (2005) Infrared and Raman spectroscopy and quantum chemistry calculation studies of C-H….O hydrogen bondings and thermal behaviour of biodegradable polyhydroxyalkanoate. J Mol Struct 744–747:35–46CrossRefGoogle Scholar
  28. 28.
    Porter Y, OK KM, Bhuvanesh NSP, Halasyamani PS (2001) Synthesis and Characterization of Te2SeO7: A Powder Second-Harmonic-Generating Study of TeO2, Te2SeO7, Te2O5, and TeSeO4. Chem Mater 13:1910–1915CrossRefGoogle Scholar
  29. 29.
    Narayana Bhat M, Dharmaprakash SM (2002) Growth of nonlinear optical γ-glycine crystals. J Cryst Growth 236:376–380CrossRefGoogle Scholar
  30. 30.
    Karakas A, Elmali A, Unver H, Svoboda I (2004) Nonlinear optical properties of some derivatives of salicylaldimine-based ligands. J Mol Struct 702:103–110CrossRefGoogle Scholar
  31. 31.
    Unver H, Karakas A, Elmali A (2004) Nonlinear optical properties, spectroscopic studies and structure of 2-hydroxy-3-methoxy-N-(2-chloro-benzyl)-benzaldehyde-imine. J Mol Struct 702:49–54CrossRefGoogle Scholar
  32. 32.
    Lee IS, Shin DM, Yoon Y, Shin SM, Chung YK (2003) Synthesis and non-linear optical properties of (alkyne)dicobalt octacarbonyl complexes and their substitution derivatives. Inorg Chim Acta 343:41–50CrossRefGoogle Scholar
  33. 33.
    Mang C, Wu K, Zhang M, Hong T, Wei Y (2004) First-priciple study on second-order optical nonlinearity of some ferrocenyl complexes. J Mol Struct (Theochem) 674:77–82CrossRefGoogle Scholar
  34. 34.
    Justin Thomas KR, Lin JT, Wen YS (1999) Synthesis, spectroscopy and structure of new push-pull ferrrocene complexes containing heteroaromatic rings (thiophene and furan) in the conjugation chain. J Organomet Chem 575:301–309CrossRefGoogle Scholar
  35. 35.
    Albert IDL, Marks TJ, Ratner MA (1998) Large molecular hyperpolarizabilities in “push-pull” porphyrins. Molecular planarity and auxiliary donor-acceptor effects. Chem Mater 10:753–762CrossRefGoogle Scholar
  36. 36.
    Zhou Y, Feng S, Xie Z (2003) Investigation nonlinear optical property of novel para-phenylenealkyne macrocycles. Opt Mater 24:667–670CrossRefGoogle Scholar
  37. 37.
    Dworczak R, Fabian WMF, Reidlinger C, Rumpler A, Schachner J, Zangger K (2002) Nonlinear optical properties of diazabutadienes and hexatrienes; experimental and computational aspects. Spectrochim Acta A 58:2135–2144CrossRefGoogle Scholar
  38. 38.
    Di Bella S, Fragala I, Ledoux I, Diaz-Garcia MA, Lacroix PG, Marks TJ (1994) Sizable second-order nonlinear optical response of donor-acceptor bis(salicylaldiminato)nickel(II) schiff base complexes. Chem Mater 6:881–883CrossRefGoogle Scholar
  39. 39.
    Prabhu SG, Rao PM, Bhat SI, Upadyaya V, Inamdar SR (2001) Growth and characterization of N-(2-Chlorophenyl)-(1-Propanamide)-a nonlinear organic crystal. J Cryst Growth 233:375–379CrossRefGoogle Scholar
  40. 40.
    Crasta V, Ravindrachary V, Bharantri RF, Gonsalves R (2004) Growth and characterization of an organic NLO crystal: 1-(4-methylphenyl)-3-(4-methoxyphenyl)-2-propen-1-one. J Crystal Growth 267:129–133CrossRefGoogle Scholar
  41. 41.
    Szafran M, Komasa A, Adamska EB (2007) Crystal and molecular structure of 4-carboxypiperidinium chloride (4-piperidinecarboxylic acid hydrochloride). J Mol Struct 827:101–107CrossRefGoogle Scholar
  42. 42.
    Jun-na L, Zhi-rang C, Shen-fang Y (2005) Study on the prediction of visible absorption maxima of azobenzene compounds. J Zhejiang Univ Sci 6B:584–590CrossRefGoogle Scholar
  43. 43.
    Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88:899–926CrossRefGoogle Scholar
  44. 44.
    Wang G, Lian F, Xie Z, Su G, Wang L, Jing X, Wang F (2002) Novel bis(8-hydroxyquinoline)phenolato–aluminum complexes for organic light-emitting diodes. Synth Met 131:1–5CrossRefGoogle Scholar
  45. 45.
    Fukui K, Yonezawa T, Shingu H (1952) A molecular orbital theory of reactivity in aromatic hydrocarbons. J Chem Phys 20:722–725CrossRefGoogle Scholar
  46. 46.
    Padmaja L, Ravikumar C, Sajan D, Hubert Joe I, Jayakumar VS, Pettit GR, Faurskov Neilsen O (2009) Density functional study on the structural conformations and intramolecular charge transfer from the vibrational spectra of the anticancer drug combretastatin-A2. J Raman Spectrosc 40:419–428CrossRefGoogle Scholar
  47. 47.
    Ravikumar C, Hubert Joe I, Jayakumar VS (2008) Charge transfer interactions and nonlinear optical properties of push-pull chromophore benzaldehyde phenylhydrazone: a vibrational approach. Chem Phys Lett 460:552–558CrossRefGoogle Scholar
  48. 48.
    Sun Q, Li Z, Zeng X, Ge M, Wang D (2005) Structures and properties of the hydrogen-bond complexes: theoretical studies for the coupling modes of the pyrazole-imidazole system. J Mol Struct (Theochem) 724:167–172CrossRefGoogle Scholar
  49. 49.
    Chai SY, Zhou R, An ZW, Kimura A, Fukuho K, Matsumura M (2005) 5-Coordinated aluminium complexes having two 2, 4-dimethyl-8-hydroxyquinoline ligands and a phenolic ligand as possible materials for white emission organic light emitting devices. Thin solid films 479:282–287CrossRefGoogle Scholar
  50. 50.
    Brooks J, Babayan Y, Lamansky S, Djurovich PI, Tsyba I, Bau R, Thompson ME (2002) Synthesis and characterization of phosphorescent cyclometalated platinum complexes. Inorg Chem 41:3055–3066CrossRefPubMedGoogle Scholar
  51. 51.
    Silverstein M, Clayton Basseler G, Morill C (1981) Spectrometric identification of organic compounds. Wiley, New yorkGoogle Scholar
  52. 52.
    Shanmugam R, Sathyanarayana DN (1984) Raman and polarized infrared spectra of pyridine-2thione. Spectrochim Acta A 40:757–761CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Kanagarathinam Saravanan
    • 1
  • Natesan Srinivasan
    • 1
  • Venugopal Thanikachalam
    • 1
  • Jayaraman Jayabharathi
    • 1
  1. 1.Department of ChemistryAnnamalai UniversityAnnamalainagarIndia

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