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Fluorescence enhancement of organic chromophore in solid state via organic–inorganic hybrid matrix: Steady state and kinetic studies

  • Original Paper: Sol-gel and hybrid materials for optical, photonic and optoelectronic applications
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Abstract

Xerogels of silica-based organic–inorganic hybrid materials consisting of covalently bound fluorophores, terthiophene and terphenylene derivatives, were fabricated and analyzed. The synthesized chromophore-containing alkoxysilane derivatives were no emission in solid state, but showed strong fluorescence in organic–inorganic hybrid materials as well as in solution. Moreover, the fluorescence quantum yield of chromophore could be further improved in organic–inorganic hybrid materials with the optimized component than that of chromophore dissolved in solution. On the other hand, the fluorescence intensity of hybrid materials decreased with increasing the concentration of chromophore in organic–inorganic hybrid materials. Obviously, the relative distance between chromophores was shortened to perturb radiative relaxation. Temperature-dependent fluorescence spectra revealed that the fluorescence of chromophore in organic–inorganic hybrid materials was temperature-independent. This result indicated the inter-chromophore interactions and intra-molecular motion have been forbidden. The kinetic measurements confirmed that the chromophore spread in organic–inorganic hybrid materials was fixed with rigid conformation. The florescence decay lifetime of chromophore also kept similar at different temperature with organic–inorganic hybrid materials skeleton. This hybrid matrix provided a platform that enhanced fluorescence of chromophore in solid state at ambient temperature.

Graphical Abstract

Emission enhancement of organic chromophores, terthiophene and terphenylene, was performed through the utilization of covalently bound silica-based organic–inorganic hybrid material (OIHM). The chromophore was no emission in solid state, but showed strong fluorescence in OIHM as well as in solution. Moreover, the fluorescence quantum yield of chromophore could be better in OIHM with optimized component than that in solution. Temperature-dependent fluorescence spectra revealed that the fluorescence of chromophore in OIHM was temperature-independent. The kinetic measurements confirmed that the chromophore spread in OIHM was fixed with rigid conformation. This OIHM system offered a useful platform to maintain the emission behavior of organic chromophores in quasi-solid state.

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References

  1. May V, Kühn O (2004) Charge and energy transfer dynamics in molecular systems. Wiley-VCH, Weinheim

    Google Scholar 

  2. Klessinger M, Michl J (1994) Excited states and photochemistry of organic molecules. VCH, Weinheim

    Google Scholar 

  3. Chen CH, Liu KY, Sudhakar S, Lim TS, Fann W, Hsu CP, Luh TY (2005) Efficient light harvesting and energy transfer in organic-inorganic hybrid multichromophoric materials. J Phys Chem B 109:17887–17891

    Article  Google Scholar 

  4. Lin CL, Chen CH, Lim TS, Fann W, Luh TY (2008) Combining light harvesting and electron transfer in silica–titania-based organic–inorganic hybrid materials. Chem Asian J 3:578–584

    Article  Google Scholar 

  5. Gomez-Romero P, Sanchez C (2004) Functional hybrid materials. Wiley-VCH, Weinheim

    Google Scholar 

  6. Kwak SY, Kim NR, Lee K, Yi J, Kim JH, Bae BS (2011) Enhancement of fluorescence and lasing properties of covalent bridged fluorescent dye in organic-inorganic hybrid materials. J Sol–Gel Sci Techn 60:137–143

    Article  Google Scholar 

  7. Grando SR, Santos FD, Gallas MR, Costa TMH, Benvenutti EV, Rodembusch FS (2012) Photophysics of aminobenzazole dyes in silica-based hybrid materials. J Sol–Gel Sci Techn 63:235–241

    Article  Google Scholar 

  8. Pletsch D, Santos FD, Rodembusch FS, Stefani V, Campo LF (2012) Bis-silylated terephthalate as a building block precursor for highly fluorescent organic-inorganic hybrid materials. New J Chem 36:2506–2513

    Article  Google Scholar 

  9. Lucenti E, Botta C, Cariati E, Righetto S, Scarpellini M, Tordin E, Ugo R (2013) New organic-inorganic hybrid materials based on perylene diimide-polyhedral oligometric silsesquioxane dyes with reduced quenching of the emission in the solid state. Dyes Pigments 96:748–755

    Article  Google Scholar 

  10. Ohtani N, Tonoi M (2014) Improved photoluminescence lifetime of organic emissive materials embedded in organic-inorganic hybrid thin films fabricated by sol-gel methods using tetraethoxysilane. Mol Cryst Liq Cryst 599:132–138

    Article  Google Scholar 

  11. Liu Y, Yang W, Liu H (2015) Azobenzene-functionalized cage silsesquioxanes as inorganic-organic hybrid, photoresponsive, nanoscale, building blocks. Chem Eur J 21:4731–4738

    Article  Google Scholar 

  12. Modiri S, Mohseni M, Mohajerani E, Kowsari E (2015) Synthesis of organic-inorganic Alq3-based hybrid material by sol-gel method. J Inorg Organomet P 25:680–686

    Article  Google Scholar 

  13. Gom M, Sato K, Tanaka K, Chujo Y (2016) Controllable intramolecular interaction of 3D arranged pi-conjugated luminophores based on a POSS scaffold, leading to highly thermally-stable and emissive materials. RSC Advances 82:78652–78660

    Google Scholar 

  14. Philippo C, Bourdolle A, Maury O, Dubois F, Boury B, Brustlein S, Brasselet S, Andraud C, Ibanez A (2011) Doped silica nanoparticles containing two-photon luminescent Eu(III) complexes for the development of water stable biolabels. J Mater Chem 21:18613–18622

    Article  Google Scholar 

  15. Seo J, Chung JW, Won JE, Park SY (2014) Photoisomeriation-induced gel-to-sol transition and concomitant fluorescence switching in a transparent supramolecular gel of a cyanostilbene derivative. Chem Sci 5:4845–4850

    Article  Google Scholar 

  16. Lin CL, Yeh MY, Chen CH, Sudhakar S, Luo SJ, Hsu YC, Huang CY, Ho KC, Luh TY (2006) Silica-titania-based organic-inorganic hybrid materials for photovoltaic applications. Chem Mater 18:4157–4162

    Article  Google Scholar 

  17. Yang XH, Giovenzana T, Field B, Jabbour GE, Sellinger A (2012) Solution processeable organic-inorganic hybrids based on pyrene functionalized mixed cubic silsesquioxanes as emitters in OLEDs. J Mater Chem 22:12689–12694

    Article  Google Scholar 

  18. Philippot C, Duboi F, Mauri M, Boury B, Prat A, Ibanez A (2012) New core-shell hybrid nanoparticles for biophotonics: fluorescent organic nanocrystals confined in organosilicate spheres. J Mater Chem 22:11370–11378

    Article  Google Scholar 

  19. Kim KH, Park SY (2016) Enhancing light-extraction efficiency of OLEDs with high- and low-refractive-index organic-inorganic hybrid materials. Org Electron 36:103–112

    Article  Google Scholar 

  20. Cho AR, Park SY (2015) Synthesis of titania- and silica-polymer hybrid materials and their application as refractive index-matched layers in touch screens. Opt Mater Express 5:690–703

    Article  Google Scholar 

  21. Daute OJ, Borras C, Borras JD, Moreau JJE (2012) Self-organisation of organosilicas: new approach for the nanostructuration of thin films and the photolithography. Actual Chimique 366:29–35

    Google Scholar 

  22. Cref G, Pichon BP, Blanc C, Maurin D, Sauvajol JL, Carcel C, Moreau JJE, Roy P, Bartlett JR, Man MWC, Bantignies JL (2013) Self-assembly of bridged silsesquioxanes: modulating structural evolution via cooperative covalent and noncovalent interactions. Langmuir 29:5581–5588

    Article  Google Scholar 

  23. Pichon BP, Scampini S, Bied C, Moreau JJE, Man MWC (2012) The influence of arylene and alkylene units on the structuring of urea-based bridged silsesquioxanes. Eur J Inorg Chem 32:5312–5322

    Article  Google Scholar 

  24. Creff G, Arrachart G, Hermet P, Wadepohl H, Almairac R, Maurin D, Sauvajol JL, Carcel C, Moreau JJE, Dieudonne P, Man MWC, Bantignies JL (2012) Investigation on the vibrational and structural properties of a self-structured bridged silsesquioxane. Phys Chem Chem Phys 14:5672–5679

    Article  Google Scholar 

  25. Chemtob A, Ni LL, Croutxe-Barghorn C, Boury B (2014) Ordered hybrids from template-free organosilane self-assembly. Chem Eur J 20:1790–1806

    Article  Google Scholar 

  26. Boury B, Corriu RJP (2003) Auto-organization in sol-gel type polycondensation: a donor to the nanosciences. Chem Rec 3:120–132

    Article  Google Scholar 

  27. Chen CH, Huang YC, Liao WC, Lim TS, Liu KL, Chen IC, Luh TY (2012) Controlling conformations in alternating dialkylsilylene-spaced donor-acceptor copolymers by a cooperative Thorpe-Ingold effect and polymer folding. Chem Eur J 18:334–346

    Article  Google Scholar 

  28. Osuka A, Maruyama K (1988) Synthesis of naphthalene-bridged porphyrin dimers and their orientation-dependent exciton coupling. J Am Chem Soc 110:4454–4456

    Article  Google Scholar 

  29. Matile S, Berova N, Nakanishi K, Fleischhauer J, Woody RW (1996) Structural studies by exciton coupled circular dichroism over a large distance: porphyrin derivatives of steroids, dimeric steroids, and brevetoxin B. J Am Chem Soc 118:5198–5206

    Article  Google Scholar 

  30. Guillet J (1985) Polymer photophysics and photochemistry. Cambridge University Press, Cambridge

    Google Scholar 

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Acknowledgements

This work was financially supported by the Ministry of Science and Technology (105-2113-M-035-002-MY2) and Feng Chia University of the Republic of China. We thank Professors Tien-Yau Luh and Tsong-Shin Lim for helping us to synthesize the corresponding monomers and use femto-second laser facilities for kinetic measurements, respectively.

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  1. Department of Chemical Engineering, Feng Chia University, Taichung, 407, Taiwan

    Chih-Hsien Chen & Yen-Ting Tsao

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  1. Chih-Hsien Chen
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Correspondence to Chih-Hsien Chen.

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Chen, CH., Tsao, YT. Fluorescence enhancement of organic chromophore in solid state via organic–inorganic hybrid matrix: Steady state and kinetic studies. J Sol-Gel Sci Technol 83, 190–196 (2017). https://doi.org/10.1007/s10971-017-4376-1

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  • DOI: https://doi.org/10.1007/s10971-017-4376-1

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