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Non-symmetrical bis-silylated precursor can (also) self-direct the assembly of Silsesquioxane films

  • Original Paper: Supramolecular materials
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Abstract

Symmetric α,ω-bis-silylated precursors are the standard building blocks of self-assembled bridged silsesquioxanes, a unique class of robust ordered nanomaterials prepared by sol-gel process without external surfactant. We report an unprecedented approach based on the utilization of a dissymmetric bis-silylated precursor, 1,2-bis(trimethoxysilyl)decane (1), in which the two alkoxy groups are carried by adjacent methylene groups. Extensive characterization—based on X-ray diffraction, real-time fourier transform infrared, electron and optical microscopy, 29Si solid-state nuclear magnetic resonance, thermogravimetry, and molecular modeling—shows surprisingly that such non-symmetrical precursor is highly conducive to achieve highly ordered lamellar mesostructure, able to sustain temperature up to 120 °C. To emphasize the effect of the alkoxy group functionality and position, comparison is made systematically with analogous silsesquioxanes derived from bis-(2) and mono-silylated (3) precursors. The sol-gel polymerization of 1 is unique by its ability to produce a homogeneous film possessing structural characteristic on multiple scales: uniform microcrystallites consisting of nanolamellar organosilica hybrid material. The most likely mesostructure consists of bilayers of slightly interpenetrated trans C8H9 chains, with a single central siloxy-hydrocarbon chain (Si2O(OH)4-C2H3) n . To permit a good lateral chain packing, the hydrocarbon chain of two adjacent silicon atoms point in opposite directions.

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Acknowledgements

Dr. Lingli Ni would like to thank the financial support from the National Natural Science Foundation of China (No. 51503072), Natural Science Foundation of Jiangsu Province (No. BK20150419) and Six Talent Peaks Project in Jiangsu Province (No. 2016XCL010).

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Authors and Affiliations

  1. Key Laboratory for Palygorskite Science and Applied Technology of Jiangsu Province, College of Chemical Engineering, Huaiyin Institute of Technology, Huaian, 223003, People’s Republic of China

    Lingli Ni

  2. Institute of Material Science of Mulhouse, CNRS, UMR 7361, University of Haute-Alsace, 3 bis rue Alfred Werner, Mulhouse Cedex, 68093, France

    Abraham Chemtob, Séverinne Rigolet, Irena Deroche, Laure Michelin & Loïc Vidal

  3. Laboratory of Photochemistry and Macromolecular Engineering, ENSCMu, University of Haute-Alsace, 3 bis rue Alfred Werner, Mulhouse Cedex, 68093, France

    Céline Croutxé-Barghorn

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  1. Lingli Ni
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  2. Abraham Chemtob
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  3. Céline Croutxé-Barghorn
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  4. Séverinne Rigolet
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  7. Loïc Vidal
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Correspondence to Lingli Ni or Abraham Chemtob.

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Ni, L., Chemtob, A., Croutxé-Barghorn, C. et al. Non-symmetrical bis-silylated precursor can (also) self-direct the assembly of Silsesquioxane films. J Sol-Gel Sci Technol 84, 222–230 (2017). https://doi.org/10.1007/s10971-017-4482-0

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  • DOI: https://doi.org/10.1007/s10971-017-4482-0

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