Manipulating single-wall carbon nanotubes by chemical doping and charge transfer with perylene dyes


Single-wall carbon nanotubes (SWNTs) are emerging as materials with much potential in several disciplines, in particular in electronics and photovoltaics. The combination of SWNTs with electron donors or acceptors generates active materials, which can produce electrical energy when irradiated. However, SWNTs are very elusive species when characterization of their metastable states is required. This problem mainly arises because of the polydispersive nature of SWNT samples and the inevitable presence of SWNTs in bundles of different sizes. Here, we report the complete and thorough characterization of an SWNT radical ion-pair state induced by complexation with a perylene dye, which combines excellent electron-accepting and -conducting features with a five-fused ring π-system. At the same time, the perylene dye enables the dispersion of SWNTs by means of ππ interactions, which gives individual SWNTs in solution. This work clears a path towards electronic and optoelectronic devices in which regulated electrical transport properties are important.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Spectroelectrochemistry of SWNT–SDBS.
Figure 2: Spectroscopic and microscopic characterization of SWNT–1.
Figure 3: Raman characterization of SWNT–SDBS and SWNT–1.
Figure 4: Visible and near-infrared fluorescence of 1, SWNT–SDBS and SWNT–1.
Figure 5: Photophysics of SWNT–1.
Figure 6: Spectroelectrochemistry of SWNT–1.


  1. 1

    Lu, W. & Lieber, C. M. Nanoelectronics from the bottom up. Nature Mater. 6, 841–850 (2007).

    CAS  Article  Google Scholar 

  2. 2

    Kauffman, D. R. & Star, A. Electronically monitoring biological interactions with carbon nanotube field-effect transistors. Chem. Soc. Rev. 37, 1197–1206 (2008).

    CAS  Article  Google Scholar 

  3. 3

    Prato, M., Kostarelos, K. & Bianco, A. Functionalized carbon nanotubes in drug design and discovery. Acc. Chem. Res. 41, 60–68 (2008).

    CAS  Article  Google Scholar 

  4. 4

    Viry, L., Derré, A., Garrigue, P., Sojic, N., Poulin, P. & Kuhn, A. Optimized carbon nanotube fiber microelectrodes as potential analytical tools. Anal. Bioanal. Chem. 389, 499–505 (2007).

    CAS  Article  Google Scholar 

  5. 5

    Campidelli, S., Meneghetti, M. & Prato, M. Separation of metallic and semiconducting single-walled carbon nanotubes via covalent functionalization, Small 3, 1672–1676 (2007).

    CAS  Article  Google Scholar 

  6. 6

    Kong, J. et al. Nanotube molecular wires as chemical sensors. Science 287, 622–625 (2000).

    CAS  Article  Google Scholar 

  7. 7

    Collins, P. G., Bradley, K., Ishigami, M. & Zettl, A. Extreme oxygen sensitivity of electronic properties of carbon nanotubes. Science 287, 1801–1804 (2000).

    CAS  Article  Google Scholar 

  8. 8

    Star, A., Joshi, V., Skarupo, S., Thomas, D. & Gabriel, J.-C. P. Gas sensor array on metal-decorated carbon nanotubes. J. Phys. Chem. B 110, 21014–21020 (2006).

    CAS  Article  Google Scholar 

  9. 9

    Kazaoui, S., Minami, N. & Jacquemin, R. Amphoteric doping of single-wall carbon-nanotube thin films as probed by optical absorption spectroscopy. Phys. Rev. B 60, 13339–13342 (1999).

    CAS  Article  Google Scholar 

  10. 10

    Carrol, D. L. et al. Effects of nanodomain formation on the electronic structure of doped carbon nanotubes. Phys. Rev. Lett. 81, 2332–2335 (1998).

    Article  Google Scholar 

  11. 11

    Zhao, Y.-Z., Hu, L., Grüner, G. & Stoddart, J. F. A tunable photosensor. J. Am. Chem. Soc. 130, 16996–17003 (2008).

    CAS  Article  Google Scholar 

  12. 12

    Guldi, D. M., Rahman, G. M. A., Sgobba, V. & Ehli, C. Multifunctional molecular carbon materials – from fullerenes to carbon nanotubes. Chem. Soc. Rev. 35, 471–487 (2006).

    CAS  Article  Google Scholar 

  13. 13

    Tasis, D., Tagmatarchis, N., Bianco, A. & Prato, M. Chemistry of carbon nanotubes. Chem. Rev. 106, 1105–1136 (2006).

    CAS  Article  Google Scholar 

  14. 14

    Paolucci, D. et al. Singling out the electrochemistry of individual single-walled carbon nanotubes in solution. J. Am. Chem. Soc. 130, 7393–7399 (2008).

    CAS  Article  Google Scholar 

  15. 15

    Herranz, M. Á. et al. Spectroscopic characterization of photolytically generated radical ion pairs in single-wall carbon nanotubes bearing surface-immobilized tetrathiafulvalenes. J. Am. Chem. Soc. 130, 66–73 (2008).

    Article  Google Scholar 

  16. 16

    Schmidt, C. D., Böttcher, C. & Hirsch A. Synthesis and aggregation properties of water-soluble Newkome-dendronized perylenetetracarboxdiimides. Eur. J. Org. Chem. 5497–5505 (2007).

  17. 17

    Bachilo, S. M. et al. Structure-assigned optical spectra of single-walled carbon nanotubes. Science 298, 2361–2366 (2002).

    CAS  Article  Google Scholar 

  18. 18

    Tomonari, Y., Murakami H. & Nakashima, N. Solubilization of single-walled carbon nanotubes by using polycyclic aromatic ammonium amphiphiles in water—strategy for the design of high-performance solubilizers. Chem. Eur. J. 12, 4027–4034 (2006).

    CAS  Article  Google Scholar 

  19. 19

    Margineanu, A. et al. Photophysics of a water-soluble rylene dye: comparison with other fluorescent molecules for biological applications. J. Phys. Chem. B 108, 12242–12251 (2004).

    CAS  Article  Google Scholar 

  20. 20

    Hayes, R. T., Wasielewski, M. R. & Gosztola, D. Ultrafast photoswitched charge transmission through the bridge molecule in a donor–bridge–acceptor system. J. Am. Chem. Soc. 122, 5563–5567 (2000).

    CAS  Article  Google Scholar 

  21. 21

    Kaletas, B. K. et al. Photoinduced electron and energy transfer processes in a bichromophoric pyrene–perylene bisimide system. J. Phys. Chem. A 108, 1900–1909 (2004).

    CAS  Article  Google Scholar 

  22. 22

    Guldi, D. M., Hungerbuehler, H. & Asmus, K. D. Radiolytic reduction of a water-soluble fullerene cluster. J. Phys. Chem. A 101, 1783–1786 (1997).

    CAS  Article  Google Scholar 

Download references


This work was carried out with financial support from the Deutsche Forschungsgemeinschaft, Cluster of Excellence ‘Engineering of Advanced Materials’, Fonds der Chemischen Industrie, the Office of Basic Energy Sciences of the US, University of Trieste, Giovani Ricercatori Program, Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, Ministero dell'Istruzione, dell'Università e della Ricerca, and Freiburg Institute for Advanced Studies (Junior Research Fellowship). We thank C. Gamboz and J. Röhrl for their assistance with TEM imaging and Raman microscopy, respectively.

Author information




C.E. performed and interpreted all steady-state and time-resolved absorption and emission measurements and the electrochemical experiments. D.M.G. interpreted the data, supervised the research and wrote the manuscript. C.O. performed and interpreted the Raman microscope and in situ Raman measurements. A.M.A. performed and interpreted AFM and TEM data. M.P. helped to analyse the data and write the manuscript. C.S. synthesized the detergents. C.B. provided expertise on the dispersion of SWNTs. F.H. supervised the chemistry and SWNT dispersion. A.H. supervised the synthesis of the detergents.

Corresponding author

Correspondence to Dirk M. Guldi.

Supplementary information

Supplementary information

Supplementary information (PDF 843 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Ehli, C., Oelsner, C., Guldi, D. et al. Manipulating single-wall carbon nanotubes by chemical doping and charge transfer with perylene dyes. Nature Chem 1, 243–249 (2009).

Download citation

Further reading


Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing