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Directed assembly of optoelectronically active alkyl–π-conjugated molecules by adding n-alkanes or π-conjugated species

Nature Chemistry volume 6, pages 690–696 (2014)Cite this article

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A Corrigendum to this article was published on 22 September 2014

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Abstract

Supramolecular assembly can yield ordered structures by taking advantage of the cumulative effect of multiple non-covalent interactions between adjacent molecules. The thermodynamic origin of many self-assembled structures in water is the balance between the hydrophilic and hydrophobic segments of the molecule. Here, we show that this approach can be generalized to use solvophobic and solvophilic segments of fully hydrophobic alkylated fullerene molecules. Addition of n-alkanes results in their assembly—due to the antipathy of C60 towards n-alkanes—into micelles and hexagonally packed gel-fibres containing insulated C60 nanowires. The addition of pristine C60 instead directs the assembly into lamellar mesophases by increasing the proportion of π-conjugated material in the mixture. The assembled structures contain a large fraction of optoelectronically active material and exhibit comparably high photoconductivities. This method is shown to be applicable to several alkyl–π-conjugated molecules, and can be used to construct organized functional materials with π-conjugated sections.

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Figure 1: Micelle formation by 1, driven by addition of n-alkane solvents.
Figure 2: Gel formation by 2, driven by addition of n-alkane solvents.
Figure 3: Structure and photoconductivity of the gel fibres formed by 2.
Figure 4: Structure, rheological properties and photoconductivity of the lamellar mesophase formed by 1, driven by addition of C60.

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Change history

  • 25 June 2014

    In the version of this Article originally published, the units on the y axes of Figs 1d and 2c were incorrect; they should have read cm–1. This has been corrected in all versions of the Article.

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Acknowledgements

This work was partially supported by KAKENHI (25620069, 25104011) from the MEXT, Japan. M.H. also thanks the Japan Society for the Promotion of Science (JSPS) and NIMS International Center for Young Scientists (ICYS) for funding. The SPring-8 synchrotron radiation experiment was performed on BL40B2 with the approval the Japan Synchrotron Radiation Research Institute (JASRI; proposal no. 2011B1548). The authors thank the beamline contact (N. Ohta, SPring8) for his help with performing SAXS measurements. The authors also thank H. Li (MPI), H. Ozawa, Y. Akasaka, M. Matsuda, J. Aimi and M. Takeuchi (NIMS) for helpful discussions, M. Ohnuma and T. Taguchi (NIMS) for use of the for Rigaku SAXS equipment and rheometer respectively, the Soft Materials Line and the MANA TSS Group at NIMS for use of spectroscopic facilities, and the STFC and Institut Laue Langevin for beam time on D11 at ILL.

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Authors and Affiliations

  1. National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, 305-0047, Japan

    Martin J. Hollamby, Brian R. Pauw & Takashi Nakanishi

  2. School of Physical and Geographical Sciences, Keele University, Keele, ST55BG, Staffordshire, UK

    Martin J. Hollamby

  3. Warsaw University of Technology, Pl. Politechniki 1, 00-661, Warsaw, Poland

    Maciej Karny & Takashi Nakanishi

  4. Department of Chemical Engineering and Chemistry and Institute of Complex Molecular Systems, Laboratory of Materials and Interface Chemistry & Soft Matter CryoTEM Research Unit, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands

    Paul H. H. Bomans & Nico A. J. M. Sommerdjik

  5. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka, 565-0871, Japan

    Akinori Saeki & Shu Seki

  6. National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, 305-8565, Japan

    Hiroyuki Minamikawa

  7. Institut Max-von-Laue-Paul-Langevin, BP 156-X, F-38042 Grenoble, Cedex, France

    Isabelle Grillo

  8. School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK

    Paul Brown & Julian Eastoe

  9. Department of Interfaces, Max Planck Institute of Colloids and Interfaces, Research Campus Golm, Potsdam, 14476, Germany

    Helmuth Möhwald

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Contributions

M.J.H. and T.N. are joint principal investigators; they designed the work, carried out research, analysed data and wrote the paper. M.K. helped to characterize the lamellar mesophases. P.H.H.B. and N.A.J.M.S. performed the cryo-TEM experiments. A.S. and S.S. performed the TRMC studies. H.Mi. contributed to the temperature-dependent XRD studies. I.G., P.B. and J.E. helped acquire the SANS data and advised on presentation and English. B.R.P. helped acquire, reduce and analyse the SAXS data. H.Mö. was involved in developing the concept and in discussions about the work. All authors discussed the results and commented on the manuscript.

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Correspondence to Martin J. Hollamby or Takashi Nakanishi.

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Hollamby, M., Karny, M., Bomans, P. et al. Directed assembly of optoelectronically active alkyl–π-conjugated molecules by adding n-alkanes or π-conjugated species. Nature Chem 6, 690–696 (2014). https://doi.org/10.1038/nchem.1977

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