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Luminescent urea cross-linked tripodal siloxane-based hybrids

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Abstract

This work reports the synthesis of novel sol–gel derived urea cross-linked tripodal siloxane-based hybrids (classed as tri-ureasils) modified by the addition of phenyltriethoxysilane (PTES) and diphenyldimethoxysilane (DPDMS). The materials were produced as transparent monoliths and thin films (thickness = 3.3–17.5 ± 0.1 μm) and characterized by X-ray diffraction, mid-infrared spectroscopy, 29Si and 13C nuclear magnetic resonance, thermogravimetric analysis, ultraviolet/visible (UV/Vis) absorption and photoluminescence spectroscopies. The role played by PTES and DPDMS as light harvesting chromophores has been discussed and quantified through emission quantum yield and UV/Vis absorption measurements. All the hybrids show efficient emission at room temperature in the blue spectral region with maximum emission quantum yield values ranging from 0.01 ± 0.001 to 0.10 ± 0.01. The highest values were found for the tri-ureasils incorporating PTES and DPDMS essentially due to an increase in the absorption coefficient (from 1.4 × 103 cm−1, for the pristine tri-ureasil, to 8.6 × 103 cm−1, for the hybrids modified by the chromophores). The existence of energy transfer between the DPDMS and PTES excited states and the hybrid host intrinsic emitting levels (NH/C=O- and siliceous-related levels) has been discussed.

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Acknowledgments

This work was financed by FEDER, COMPETE, and FCT (PEst-C/CTM/LA0011/2011, PTDC/CTM/101324/2008, PTDC/CTMBPC/112774/2009) and the Portuguese National NMR Network (RNRMN). PPL acknowledges FCT for a grant (SFRH/BPD/34365/2006).

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Authors and Affiliations

  1. Physics Department and CICECO, University of Aveiro, 3810-193, Aveiro, Portugal

    Vânia T. Freitas, P. P. Lima, R. A. S. Ferreira & L. D. Carlos

  2. Instituto de Telecomunicações, University of Aveiro, 3810-193, Aveiro, Portugal

    E. Pecoraro

  3. Chemistry Department and CQ-VR, University of Trás-os-Montes and Alto Douro, 5001-801, Vila Real, Portugal

    M. Fernandes & V. de Zea Bermudez

Authors
  1. Vânia T. Freitas
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  2. P. P. Lima
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  3. R. A. S. Ferreira
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  4. E. Pecoraro
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  5. M. Fernandes
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  6. V. de Zea Bermudez
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  7. L. D. Carlos
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Correspondence to L. D. Carlos.

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Freitas, V.T., Lima, P.P., Ferreira, R.A.S. et al. Luminescent urea cross-linked tripodal siloxane-based hybrids. J Sol-Gel Sci Technol 65, 83–92 (2013). https://doi.org/10.1007/s10971-012-2770-2

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  • DOI: https://doi.org/10.1007/s10971-012-2770-2

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