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Preparation and photophysical properties of monomeric liquid-crystalline azo-dyes embedded in bulk and film SiO2-sonogel glasses

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Abstract

SiO2-based bulk and film sol–gel hybrid materials were prepared with a family of novel liquid crystalline (LC) amphiphilic azo-dyes bearing oligo(ethylene glycol) spacers (named here RED-PEG-n, n = 2, 3, 4, 6). The catalyst-free-sonogel route was implemented to produce optically active hybrid monoliths and spin-coated films with these materials. Comprehensive morphological, thermal, photo-acoustic and spectroscopic sample characterizations were performed in order to elucidate the physical properties of these novel compounds within the sonogel environment. Film samples were also studied via the nonlinear optical (NLO) second harmonic generation (SHG)-Maker fringes technique. Results show that the chromophores were homogeneously embedded within the highly pure SiO2-sonogel network, showing a clear thermotropic mesogenic behavior. The push–pull structure of the implemented azo-dyes allowed effective electrically-induced monomeric alignment within the sonogel confinement; thus, stable quadratic NLO-SHG-activity in the organic–inorganic film samples was achieved despite the lack of glass transition temperature (T g ) of the guest LC-compounds.

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Notes

  1. The TEOS/H2O mixture obtained after sonication is a homogeneous opaque suspension containing both the sonochemically reacted and unreacted molecular species from the constituting reactants. Note that despite the fact that the cooling system is always on during sonication, the intermittent US-irradiation sequences of 5 s allow the system to cool down in order to avoid excessive reaction temperatures promoted by intense US-irradiation. These intermittent irradiation sequences also provide adequate silence periods for recombination of the formed molecular species, giving rise to an increase of hydrolyzed Si-based molecular compounds, which form after condensation/polymerization a stable SiO2 glassy network [37].

  2. The slow drying process of the samples performed at room temperature has proven to be efficient in order to produce quality film structures with adequate morphology suitable for optical characterizations as verified by AFM-microscopy. On the other hand, it has also been proven that negligible water residuals remain within the porous sonogel glassy structure [37], which are in any case eliminated as the film samples are heated for Corona-poling processing or are non-active for quadratic NLO-SHG effects.

  3. Note that for the n = 6 compound, the spectral and other experimental data are not reported (see below) since the optical quality of both, bulk and film hybrid samples was not acceptable; i.e., the n = 6 based hybrids exhibit strong light scattering and poor bulk and film quality which also affects the accuracy of the NLO-characterizations at the fundamental and SHG wavelengths.

  4. Thermodynamic phase-transitions only detected on cooling the sample below the melting temperature.

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Acknowledgments

The authors are grateful to Dr. Neil Bruce for English revision of the manuscript. This work was supported by projects SEP-CONACyT (Grant: U-49846-F) and PAPIIT-DGAPA-UNAM (Grant: IN-115508). O G Morales-Saavedra also acknowledges financial support from the DAAD academic organization (Germany). E. Rivera thanks PAPIIT-DGAPA-UNAM (Grant: IN-105610).

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Authors and Affiliations

  1. Nonlinear Optics Lab. Centro Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, CCADET-UNAM, Circuito Exterior S/N, Ciudad Universitaria C.P. 04510, Mexico, DF, México

    V. Torres-Zúñiga, O. G. Morales-Saavedra, R. Castañeda-Guzmán, J. G. Bañuelos & R. Ortega-Martínez

  2. Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, IIM-UNAM, Circuito Exterior, Ciudad Universitaria C.P. 04510, Mexico, DF, México

    E. Rivera

Authors
  1. V. Torres-Zúñiga
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  2. O. G. Morales-Saavedra
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  3. E. Rivera
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  4. R. Castañeda-Guzmán
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  5. J. G. Bañuelos
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  6. R. Ortega-Martínez
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Correspondence to O. G. Morales-Saavedra.

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Torres-Zúñiga, V., Morales-Saavedra, O.G., Rivera, E. et al. Preparation and photophysical properties of monomeric liquid-crystalline azo-dyes embedded in bulk and film SiO2-sonogel glasses. J Sol-Gel Sci Technol 56, 7–18 (2010). https://doi.org/10.1007/s10971-010-2265-y

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  • DOI: https://doi.org/10.1007/s10971-010-2265-y

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