Abstract
The discovery and large-scale synthesis of fullerenes have aroused interdisciplinary interest in these closed-cage molecules1,2,3,4,5,6. C60 can be photopolymerized into a form in which the cages are thought to be linked by cyclic C4 units in a [2 + 2] cycloaddition7, provoking theoretical studies of the C60 dimer8,9,10,11,12,13,14,15, the smallest subunit of such a polymer. The C60 dimers C120O (refs 16, 17), C121H2( ref. 17) and C120O2(ref. 18) have been reported, in which the two C60molecules are linked by, respectively, a furan group, a cyclopentane ring and a cyclobutane ring plus two oxygen bridges; but the simplest dimer, C120linked by a cyclobutane ring alone, has not so far been observed. We now report that this dumb-bell-shaped molecule can be synthesized by a solid-state mechanochemical reaction of C60 with potassium cyanide. Our X-ray structural analysis shows that the C4 ring connecting the cages is square rather than rectangular—the latter is predicted theoretically8,9,13,14,15. The dimer dissociates cleanly into two C60 molecules on heating or one-electron reduction, but in the gas phase during mass-spectrometric measurements it undergoes successive loss of C2 units, shrinking to even-numbered fullerenes such as C118 and C116 in a sequence similar to that seen for other large fullerenes19,20.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Acc. Chem. Res. (spec. iss. on buckminsterfullerenes) 25, 97–176 (1992).
Billups, W. E. & Ciufolini, M. A. (eds Buckminsterfullerenes (VCH, New York, Weinheim, (1993)).
Kroto, H. W., Fischer, J. E. & Cox, D. E. (eds The Fullerenes (Pergamon, Oxford, (1993)).
Prassides, K. (ed. Physics and Chemistry of the Fullerenes (NATO ASI Ser., Kluwer Academic, Dordrecht, (1994)).
Kuzmany, S., Fink, J., Mehring, M. & Roth, S. (eds Progress in Fullerene Research (World Scientific, Singapore, (1994 )).
Taylor, R. (ed. The Chemistry of Fullerenes (World Scientific, Singapore, ( 1995)).
Rao, A. M. et al. Photoinduced polymerization of solid C60films. Science 259, 955–957 ( 1993).
Strout, D. L. et al. Atheoretical study of buckminsterfullerene reaction products C60+ C60. Chem. Phys. Lett. 214 , 576–582 (1993).
Matsuzawa, N., Ata, M., Dixon, D. A. & Fitzgerald, G. Dimerization of C60: the formation of dumbbell-shaped C120. J. Phy. Chem. 98, 2555–2563 (1994).
Menon, M., Subbaswamy, K. R. & Sawtarie, M. Structure and properties of C60 dimers by generalized tight-binding molecular dynamics. Phys. Rev. B 49, 13966–13969 (1994).
Adams, G. B., Page, J. B., Sankey, O. F. & O'Keeffe, M. Polymerized C60 studied by first-principles molecular dynamics. Phys. Rev. B 50, 17471– 17479 (1994).
Porezag, D., Pederson, M. R., Frauenheim, T. & Köhler, T. K. Structure, stability, and vibrational properties of polymerized C60. Phys. Rev. B 52, 14963– 14970 (1995).
Kürti, J. & Németh, K. Structure and energetics of neutral and negatively charged C60dimers. Chem. Phys. Lett. 256, 119–125 (1996).
Scuseria, G. E. What is the lowest-energy isomer of the C60 dimer? Chem. Phys. Lett. 257, 583–586 (1996).
Osawa, S., Sakai, M. & Osawa, E. Nature of cyclobutane bonds in the neutral [2 + 2] dimer of C60. J.Phys. Chem. A 101, 1378–1383 (1997).
Lebedkin, S., Ballenweg, S., Gross, J., Taylor, R. & Krätschmer, W. Synthesis of C120O: a new dimeric [60]fullerene derivative. Tetrahedr. Lett. 36, 4971– 4974 (1995).
Smith, A. B., Tokuyama, H., Strongin, R. M., Furst, G. T. & Romanow, W. J. Synthesis of oxo- and methylene-bridged C60 dimers, the first well-characterized species containing fullerene-fullerene bonds. J. Am. Chem. Soc. 117, 9359– 9360 (1995).
Gromov, A. et al. C120O2: The first [60]fullerene dimer with cages bis-linked by furanoid bridges. J.Chem. Soc. Chem. Commun. 209–210 (1997).
Yeretzian, C., Hansen, K., Diederich, F. & Whetten, R. L. Coalescence reactions of fullerenes. Nature 359, 44–47 (1992).
Ata, M., Takahashi, N. & Nojima, K. Mass peak assignment for C60 polymer generated in an Ar plasma. J. Phys. Chem. 98, 9960 –9965 (1994).
Wang, G.-W., Murata, Y., Komatsu, K. & Wan, T. S. M. The solid-phase reaction of [60]fullerene: novel addition of organozinc reagents. J. Chem. Soc. Chem. Commun. 2059–2060 (1996).
Braun, T. et al. Mechanochemistry: a novel approach to the synthesis of fullerene compounds. Water soluble buckminsterfullerene-γ-cyclodextrin inclusion complexes via a solid-solid reaction. Solid State Ionics 74, 47–51 (1994).
Keshavarz-K., M., Knight, B., Srdanov, G. & Wudl, F. Cyanodihydrofullerenes and dicyanodihydrofullerene: the first polar solid based on C60. J. Am. Chem. Soc. 117, 11371– 11372 (1995).
Persson, P.-A. et al. NMR and Raman characterization of pressure polymerized C 60. Chem. Phys. Lett. 258, 540– 546 (1996).
Goze, C. et al. High-resolution 13C NMR studies of high-pressure-polymerized C60: evidence for the [2 + 2] cycloaddition structure in the rhombohedral two-dimensional C60 polymer. Phys. Rev. B 54, R3676–R3678 (1996).
Ishida, T., Shinozuka, K., Nogami, T., Sasaki, S. & Iyoda, M. First X-ray structural determination of fullerene [2 + 2] cycloadduct. Chem. Lett. 317– 318 (1995).
Wang, Y., Holden, J. M., Bi, X.-X. & Eklund, P. C. Thermal decomposition of polymeric C60. Chem. Phys. Lett. 217, 413–417 (1994).
Yamawaki, H. et al. Infrared study of vibrational property and polymerization of C60 and C70under pressure. J. Phys. Chem. 97, 11161–11163 ( 1993).
Núñez-Regueiro, M., Marques, L., Hodeau, J.-L., Béthoux, O. & Perroux, M. Polymerized fullerene structures. Phys. Rev. Lett. 74, 278–281 (1995).
Bingel, C. Cyclopropanierung von Fullerenen. Chem. Ber. 126, 1957–1959 (1993).
March, J. Advanced Organic Chemistry4th edn 969–970 (Wiley, New York, (1992)).
Sun, Y.-P., Ma, B., Bunker, C. E. & Liu, B. All-carbon polymers (polyfullerenes) from photochemical reactions of fullerene clusters in room-temperature solvent mixtures. J. Am. Chem. Soc. 117, 12705–12711 (1995).
Acknowledgements
We thank K. Yamamoto of Power Reactor and Nuclear Fuel Development Corporation for measuring FT ICR MS spectra; S. Sugiura for the use of a 13C NMR spectrometer; Y.Tsujii for assistance with DSC measurements; and S. F. Nelsen (Univ. Wisconsin) and K. Tamao for discussions and encouragement. This work was supported by the Japan Society for the Promotion of Science and the Ministry of Education, Science and Culture, Japan.
Author information
Authors and Affiliations
Corresponding author
Supplementary information
Rights and permissions
About this article
Cite this article
Wang, GW., Komatsu, K., Murata, Y. et al. Synthesis and X-ray structure of dumb-bell-shaped C120. Nature 387, 583–586 (1997). https://doi.org/10.1038/42439
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/42439
This article is cited by
-
Synthesis of inter-[60]fullerene conjugates with inherent chirality
Nature Communications (2024)
-
Sublimed C60 for efficient and repeatable perovskite-based solar cells
Nature Communications (2024)
-
Long-range ordered porous carbons produced from C60
Nature (2023)
-
Fully conjugated azacorannulene dimer as large diaza[80]fullerene fragment
Nature Communications (2022)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
