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Template synthesis of precisely monodisperse silica nanoparticles within self-assembled organometallic spheres

Nature Chemistry volume 2, pages 25–29 (2010)Cite this article

Abstract

One of the key challenges in materials science is to control the size and shape of inorganic nanoparticles with a high degree of precision, as these parameters have a significant influence on the nanoparticles' properties and potential applications. Here, we describe the preparation of highly monodisperse silica nanoparticles smaller than 5 nm in diameter by using self-assembled, hollow, spherical compounds as ‘endo-templates’. These coordination complexes with pendant sugar groups lining their interiors—assembled from 12 metal ions and 24 bis-pyridyl ligands containing glucose substituents—acted as structurally well-defined templates for the sol–gel condensation of alkoxysilanes. The polydispersities of the silica nanoparticles made with this method approached unity, with Mw/Mn < 1.01. The component ligands are modified easily, which enables an accurate expansion of the coordination complex and the subsequent control of the monodisperse silica nanoparticles that span molecular weights of 5,000 to 31,000 Da (corresponding to 2–4 nm in diameter). This method could be applicable to the preparation of other inorganic nanoparticles.

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Figure 1: Synthesis of silica nanoparticles within spheres 2.
Figure 2: 1H NMR spectra (500 MHz, 300 K, DMSO-d6:CDCl3 = 1:9) of sphere 2a and 2a⊃silica.
Figure 3: Structural analyses of silica nanoparticles within spherical templates.
Figure 4: Molecular structures of spheres 2a,c that contain silica nanoparticles.

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Acknowledgements

We thank M. Kawano for supporting the synchrotron X-ray crystallographic analysis at Photon Factory-Advanced Ring for Pulse X-rays of the High Energy Accelerator Research Organization. This work was supported by the Core Research for Evolution Science and Technology project of the Japan Science and Technology Agency, for which M.F. is the principal investigator, and also in part by the Global COE Program (Chemistry Innovation through Cooperation of Science and Engineering), Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. A part of this work was conducted in the Center for Nano Lithography & Analysis, The University of Tokyo, supported by MEXT, Japan. This work was approved by the Photon Factory Program Advisory Committee.

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Authors and Affiliations

  1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

    Kosuke Suzuki, Sota Sato & Makoto Fujita

  2. Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

    Makoto Fujita

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  1. Kosuke Suzuki
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  2. Sota Sato
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  3. Makoto Fujita
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Contributions

M.F. designed and directed the project and wrote the manuscript. K.S. performed the experimental work and wrote the manuscript. S.S. contributed to the data analysis.

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Correspondence to Makoto Fujita.

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The authors declare no competing financial interests.

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Suzuki, K., Sato, S. & Fujita, M. Template synthesis of precisely monodisperse silica nanoparticles within self-assembled organometallic spheres. Nature Chem 2, 25–29 (2010). https://doi.org/10.1038/nchem.446

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