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Photophysics of aminobenzazole dyes in silica-based hybrid materials

Journal of Sol-Gel Science and Technology volume 63, pages 235–241 (2012)Cite this article

Abstract

In this work two aminobenzazole derivatives (5-AHBT and 5-AHBI) were dispersed in silica-based hybrid materials with different surface hydrophobicity, which were obtained by the sol–gel process using tetraethylorthosilicate as inorganic precursor and dimethyldimethoxysilane as organic precursor, with a molar percent of organic precursor changing from 0 to 50%. The photophysics of the obtained doped silica hybrid materials was investigated by means ultraviolet–visible diffuse reflectance and steady-state fluorescence emission spectroscopy in the solid state. The materials present absorption maxima located around 353 and 318 nm when doped with 5-AHBT and 5-AHBI, respectively. The red shifted absorption maxima of the 5-AHBT can be explained by the better electron delocalization allowed by the sulfur atom in relation to the nitrogen. The fluorescence emission spectra are located in the blue-green regions and the high Stokes shift indicates that the ESIPT mechanism occurs in the excited state for both dyes. The photophysical behavior of 5-AHBT shows that this dye is more affected by the matrix polarity due to specific interactions that take place in the ground state.

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References

  1. Avnir D (1995) Organic chemistry within ceramic matrices: doped sol–gel materials. Acc Chem Res 28:328–334

    Article  CAS  Google Scholar 

  2. Mehdi A, Reye C, Corriu R (2011) From molecular chemistry to hybrid nanomaterials. Design and functionalization. Chem Soc Rev 40:563–574

    Article  CAS  Google Scholar 

  3. Grando SR, Pessoa CM, Gallas MR, Costa TMH, Rodembusch FS, Benvenutti EV (2009) Modulation of the ESIPT emission of benzothiazole type dye incorporated in silica-based hybrid materials. Langmuir 25:13219–13223

    Article  CAS  Google Scholar 

  4. Keeling-Tucker T, Brennan JD (2001) Fluorescent probes as reporters on the local structure and dynamics in sol–gel-derived nanocomposite materials. Chem Mater 13:3331–3350

    Article  CAS  Google Scholar 

  5. Brinker CJ, Scherer GW (1990) Sol–gel science. Acad Press, NewYork

    Google Scholar 

  6. Lacatusu I, Badea N, Bojin D, Iosub S, Meghea A (2009) Novel fluorescence nano structured materials obtained by entrapment of an ornamental bush extract in hybrid silica glass. J Sol–gel Sci Technol 51:84–91

    Article  CAS  Google Scholar 

  7. Nedelcev T, Krupa I, Hrdlovic P, Kollar J, Chorvat D, Lacik I (2010) Silica hydrogel formation and aging monitored by pyrene-based fluorescence probes. J Sol–gel Sci Technol 55:143–150

    Article  CAS  Google Scholar 

  8. Unger B, Rurack K, Muller R, Resch-Genger U, Buttke K (2000) Effects of the sol–gel processing on the fluorescence properties of laser dyes in tetraethoxysilane derived matrices. J Sol–gel Sci Technol 19:799–802

    Article  CAS  Google Scholar 

  9. Reisfeld R (2001) Prospects of sol–gel technology towards luminescent materials. Opt Mater 16:1–7

    Article  CAS  Google Scholar 

  10. Cui YJ, Yu JC, Gao JK, Wang ZY, Qian GD (2009) Synthesis and luminescence behavior of inorganic-organic hybrid materials covalently bound with pyran-containing dyes. J Sol–gel Sci Technol 52:362–369

    Article  CAS  Google Scholar 

  11. Hoffmann HS, Stefani V, Benvenutti EV, Costa TMH, Gallas MR (2011) Fluorescent silica hybrid materials containing benzimidazole dyes obtained by sol–gel method and high pressure processing. Mater Chem Phys 126:97–101

    Article  CAS  Google Scholar 

  12. Wallington SA, Pilon C, Wright JD (1997) Sol–gel composites for optical sensing of solvents. J Sol–gel Sci Technol 8:1127–1132

    CAS  Google Scholar 

  13. Sanz-Menez N, Monnier V, Colombier I, Baldeck PL, Irie M, Ibanez A (2011) Photochromic fluorescent diarylethene nanocrystals grown in sol–gel thin films. Dyes Pigm 89:241–245

    Article  CAS  Google Scholar 

  14. Rodembusch FS, Leusin FP, Campo LF, Stefani V (2007) Excited state intramolecular proton transfer in amino 2-(2′-hydroxyphenyl)benzazole derivatives: effects of the solvent and the amino group position. J Lumin 126:728–734

    Article  CAS  Google Scholar 

  15. Etaiw SE-DH, Fayed TA, Saleh NZ (2006) Photophysics of benzazole derived push-pull butadienes: a highly sensitive fluorescence probes. J Photochem Photobiol A Chem 177:238–247

    Article  CAS  Google Scholar 

  16. Fayed TA, Etaiw SE-DH, Khatab HM (2005) Excited state properties and acid-base equilibria of trans-2-styrylbenzoxazoles. J Photochem Photobiol A Chem 170:97–103

    Article  CAS  Google Scholar 

  17. Yoshihara T, Druzhinin SI, Zachariasse KA (2004) Fast intramolecular charge transfer with a planar rigidized electron donor/acceptor molecule. J Am Chem Soc 126:8535–8539

    Article  CAS  Google Scholar 

  18. Santos FS, Costa TMH, Stefani V, Gonçalves PFB, Descalzo RR, Benvenutti EV, Rodembusch FS (2011) Synthesis, characterization, and spectroscopic investigation of benzoxazole conjugated Schiff bases. J Phys Chem A 115:13390–13398

    Google Scholar 

  19. Dey JK, Dogra SK (1991) Solvatochromism and prototropism in 2-(aminophenyl) benzothiazoles. Bull Chem Soc Jpn 64:3142–3152

    Article  CAS  Google Scholar 

  20. Santra S, Dogra SK (1998) Excited-state intramolecular proton transfer in 2-(2′-aminophenyl) benzimidazole. Chem Phys 226:285–296

    Article  CAS  Google Scholar 

  21. Costa TMH, Gallas MR, Benvenutti EV, da Jornada JAH (1997) Infrared and thermogravimetric study of high pressure consolidation in alkoxide silica gel powders. J Non-Cryst Solids 220:195–201

    Article  CAS  Google Scholar 

  22. Almeida RM, Pântano CG (1990) Structural investigation of silica-gel films by infrared-spectroscopy. J Appl Phys 68:4225–4232

    Article  CAS  Google Scholar 

  23. Wood DL, Rabinovich EM (1989) Study of alkoxide silica-gels by infrared-spectroscopy. Appl Spectrosc 43:263–267

    Article  CAS  Google Scholar 

  24. Colthup NB, Daly LH, Wiberley SE (1975) Introduction to infrared and raman spectroscopy. Academic Press, New York

    Google Scholar 

  25. Bellamy LJ (1975) The infrared spectra of complex molecules. Chapman and Hall, New York

    Google Scholar 

  26. Baker GA, Pandey S, Maziarz EP, Bright FV (1999) Toward tailored xerogel composites: local dipolarity and nanosecond dynamics within binary composites derived from tetraethylorthosilane and ORMOSILs, oligomers or surfactants. J Sol–gel Sci Technol 15:37–48

    Article  CAS  Google Scholar 

  27. Christoff M, Silveira NP, Samios D (2001) Fluorescence and light scattering studies on the aggregation of sodium cholate in the presence of low molecular weight poly (ethylene oxide). Langmuir 17:2885–2888

    Article  CAS  Google Scholar 

  28. Campo LF, Sanchez M, Stefani V (2006) Spectral properties of amorphous silica (SiO2) and mesoporous structured silicates (MCM-41 and ITQ-6) functionalized with ESIPT chromophores. J Photochem Photobiol A Chem 178:26–32

    Article  CAS  Google Scholar 

  29. Douhal A, Amat-Guerri F, Lillo MP, Acuña AU (1994) Proton-transfer spectroscopy of 2-(2′-hydroxyphenyl)imidazole and 2-(2′-hydroxyphenyl) benzimidazole dyes. J Photochem Photobiol A Chem 78:127–138

    Article  CAS  Google Scholar 

  30. Vazquez SR, Rodriguez MCR, Mosquera M, Rodriguez-Prieto F (2007) Excited-state intramolecular proton transfer in 2-(3′-hydroxy-2′-pyridyl) benzoxazole. Evidence of coupled proton and charge transfer in the excited state of some o-hydroxyarylbenzazoles. J Phys Chem A 111:1814–1826

    Article  CAS  Google Scholar 

  31. Mordzinski A, Grabowska A, Kuhnle W, Krowczynski A (1983) Intramolecular single and double proton-transfer in benzoxazole derivatives. Chem Phys Lett 101:291–296

    Article  CAS  Google Scholar 

  32. Mordzinski A (1988) Polyethylene as a medium for eliminating the solvent perturbation in intramolecular proton-transfer systems. Chem Phys Lett 150:254–258

    Article  CAS  Google Scholar 

  33. Zachariasse KA, Grobys M, von der Haar T, Hebecker A, Il’ichev YV, Jiang Y-B, Morawski O, Kühnle W (1996) Intramolecular charge transfer in the excited state. Kinetics and configurational changes. J Photochem Photobiol A Chem 102:59–70

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  35. Lakowicz JR (2006) Solvent and environmental effects. Principles of fluorescence spectroscopy. Springer, New York, NY

    Book  Google Scholar 

  36. Lumbroso H, Liegeois C, Pappalardo GC, Grassi A (1982) A theoretical and experimental dipole-moment study of annular tautomerism in tetrazole. J Mol Struct 82:283–294

    Article  CAS  Google Scholar 

  37. Ogretir C, Yarligan S, Berber H, Arslan T, Topal S (2003) A theoretical study of substituent effects on tautomerism of 2-hydroxybenzimidazoles. J Mol Model 9:390–394

    Article  Google Scholar 

  38. Rodembusch FS, Buckup T, Segala M, Tavares L, Correia RRB, Stefani V (2004) First hyperpolarizability in a new benzimidazole derivative. Chem Phys 305:115–121

    Article  CAS  Google Scholar 

  39. Grabowski SJ (2001) An estimation of strength of intramolecular hydrogen bonds—ab initio and AIM studies. J Mol Struct 562:137–143

    Article  CAS  Google Scholar 

  40. Gilli P, Bertolasi V, Pretto L, Ferretti V, Gilli G (2004) Covalent versus electrostatic nature of the strong hydrogen bond: discrimination among single, double, and asymmetric single-well hydrogen bonds by variable-temperature X-ray crystallographic methods in beta-diketone enol RAHB systems. J Am Chem Soc 126:3845–3855

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank Conselho Nacional de Desenvolvimento Científico e Tecnológico, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior and Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul for financial support and Instituto Nacional de Inovação em Diagnósticos para a Saúde Pública.

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Authors and Affiliations

  1. LSS—Laboratório de Sólidos e Superfícies, Universidade Federal do Rio Grande do Sul, Avenida Bento Gonçalves, 9500, CP 15003, Porto Alegre-RS, CEP 91501-970, Brazil

    Silvia Regina Grando, Fabiano da Silveira Santos, Tania Maria Haas Costa & Edilson Valmir Benvenutti

  2. LNMO—Laboratório de Novos Materiais Orgânicos, Universidade Federal do Rio Grande do Sul, Avenida Bento Gonçalves, 9500, CP 15003, Porto Alegre-RS, CEP 91501-970, Brazil

    Fabiano da Silveira Santos & Fabiano Severo Rodembusch

  3. LAPMA—Laboratório de Altas Pressões e Materiais Avançados, Universidade Federal do Rio Grande do Sul, Avenida Bento Gonçalves, 9500, CP 15003, Porto Alegre-RS, CEP 91501-970, Brazil

    Márcia Russman Gallas & Tania Maria Haas Costa

Authors
  1. Silvia Regina Grando
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  2. Fabiano da Silveira Santos
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  3. Márcia Russman Gallas
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  4. Tania Maria Haas Costa
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  5. Edilson Valmir Benvenutti
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  6. Fabiano Severo Rodembusch
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Correspondence to Edilson Valmir Benvenutti or Fabiano Severo Rodembusch.

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Grando, S.R., da Silveira Santos, F., Gallas, M.R. et al. Photophysics of aminobenzazole dyes in silica-based hybrid materials. J Sol-Gel Sci Technol 63, 235–241 (2012). https://doi.org/10.1007/s10971-012-2720-z

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