Formation and reinforcement of clusters composed of C60 molecules
© Kurosu et al; licensee Springer. 2011
Received: 25 August 2010
Accepted: 12 January 2011
Published: 12 January 2011
We carry out two experiments: (1) the formation of clusters composed of C60 molecules via self-assembly and (2) the reinforcement of the clusters. Firstly, clusters such as fibres and helices composed of C60 molecules are produced via self-assembly in supercritical carbon dioxide. However, C60 molecules are so weakly bonded to each other in the clusters that the clusters are broken by the irradiation of electron beams during scanning electron microscope observation. Secondly, UV photons are irradiated inside a chamber in which air is filled at 1 atm and the above clusters are placed, and it was found that the clusters are reinforced; that is, they are not broken by electron beams any more. C60 molecules located at the surface of the clusters are oxidised, i.e. C60O n molecules, where n = 1, 2, 3 and 4, are produced according to time-of-flight mass spectroscopy. It is supposed that oxidised C60 molecules at the surface of the clusters may have an important role for the reinforcement, but the actual mechanism of the reinforcement of the clusters has not yet been clearly understood and therefore is an open question.
It is known that clusters composed of C60 molecules such as chains and sheets can be formed by polymerising C60 molecules via the irradiation of photons [1–13], application of high pressure and/or high temperature [3, 5, 6, 14–17], or introduction of foreign atoms or molecules [18–20]. It is also known that C60 molecules can be modified with oxygen atoms and molecules [21–30].
The gas-liquid coexistence curves terminate at the critical points . Incident light cannot penetrate fluids as they approach their critical points, known as critical opalescence, due to the formation of large molecular clusters . It was recently shown that fibres, fibre networks, sheets and helices composed of C60 molecules were self-assembled by leaving C60 crystals in ethane, xenon or carbon dioxide under supercritical conditions for 24 h . Those structures were formed via van der Waals interactions between C60 and the fluids' molecules.
In this letter, we create clusters composed of C60 molecules via self-assembly in supercritical carbon dioxide and reinforce the clusters by attaching oxygen atoms to the surface of C60 molecules.
We will be investigating the mechanism of the reinforcement of the clusters, that is, the role of oxidised C60 molecules (C60O n ) located at the surface of the clusters, in the reinforcement process in detail, carrying out quantum mechanical calculations. We will also be measuring the electric, electronic, mechanical and thermal properties of the fibres and helices so that the clusters may be utilised for the development of nano electron devices, nano/microelectromechanical systems and micro-total analysis systems.
We carried out two experiments: (1) Crystals composed of C60 molecules were placed in supercritical carbon dioxide (36.0°C), and it was found that fibres, fibre networks and helices composed of C60 molecules were self-assembled. Since C60 molecules in the clusters were bonded to each other via van der Waals interactions , the clusters were easily broken by the irradiation of electron beams during the SEM observation. (2) The clusters were placed in another chamber filled with air at 1 atm and irradiated with UV photons. Oxygen molecules were dissociated by UV photons, C60 molecules at the surface of the clusters were oxidised, and C60O n molecules were created. The clusters were not broken by the electron beams any more. It is supposed that C60O n molecules located at the surface of the clusters may have an important role in the reinforcement process, but the actual mechanism of the reinforcement of the clusters has not yet been clearly understood and therefore is an open question.
Part of the present study has been supported by a Grant for High-Tech Research Centres organised by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. T. Fukuda would like to thank MEXT for their financial support.
- Eklund PC, Rao AM, Zhou P, Wang Y, Holden JM: Photochemical transformation of C 60 and C 70 films. Thin Solid Films 1995, 257: 185.View Article
- Rao CNR, Govindaraj A, Aiyer HN, Seshadri R: Polymerization and pressure-induced amorphization of C 60 and C 70 . J Phys Chem 1995, 99: 16814.View Article
- Rao AM, Eklund PC, Venkateswaran UD, Tucker J, Duncan MA, Bendele GM, Stephens PW, Hodeau J-L, Marques L, Núñez-Regueiro M, Bashkin IO, Ponyatovsky EG, Morovsky AP: Properties of C 60 polymerized under high pressure and temperature. Appl Phys A 1997, 64: 231.View Article
- Onoe J, Takeuchi K: How many [2+2] four-membered rings are formed on a C 60 molecule when photopolymerization is saturated? Phys Rev Lett 1997, 79: 2987.View Article
- Rao AM, Eklund PC, Hodeau J-L, Marques L, Nunez-Regueiro M: Infrared and Raman studies of pressure-polymerized C 60 s. Phys Rev B 1997, 55: 4766.View Article
- Onoe J, Takeuchi K: Photo-induced coalescence of C 60 molecules in a potassium-doped C 60 film: mass spectral evidence. J Mass Spectrom 1998, 33: 387.View Article
- Wågberg T, Jacobsson P, Sundqvist B: Comparative Raman study of photopolymerized and pressure-polymerized C 60 films. Phys Rev B 1999, 60: 4535.View Article
- Fujitsuka M, Fujiwara K, Murata Y, Uemura S, Kunitake M, Ito O, Komatsu K: Properties of photoexcited states of C 180 , a triangle trimer of C 60 . Chem Lett 2001, 5: 384.View Article
- Dunsch L, Rapta P, Gromov A, Staško A: In situ ESR/UV-vis-NIR spectroelectrochemistry of C 60 and its dimers C 120 , C 120 O and C 120 OS. J Electroanal Chem 2003, 547: 35.View Article
- Onoe J, Nakayama T, Aono M, Hara T: Electrical properties of a two-dimensionally hexagonal C 60 photopolymer. J Appl Phys 2004, 96: 443.View Article
- Karachevtsev VA, Mateichenko PV, Nedbailo NY, Peschanskii AV, Plokhotnichenko AM, Vovk OM, Zubarev EN, Rao AM: Effective photopolymerization of C 60 films under simultaneous deposition and UV light irradiation: Spectroscopy and morphology study. Carbon 2004, 42: 2091.View Article
- Alvarez-Zauco E, Sobral H, Basiuk EV, Saniger-Blesa JM, Villagrán-Muniz M: Polymerization of C 60 fullerene thin films by UV pulsed laser irradiation. Appl Surf Sci 2005, 248: 243.View Article
- Yamamoto H, Iwata N, Hashimoto R, Ando S: Photon-assisted synthesis of C 60 polymers by laser irradiation. Appl Surf Sci 2007, 253: 7977.View Article
- Oszlanyi G, Forro L: Two-dimensional polymer of C 60 . Solid State Commun 1995, 93: 265.View Article
- Persson P-A, Edlund U, Jacobsson P, Johnels D, Soldatov A, Sundqvist B: NMR and Raman characterization of pressure polymerized C 60 . Chem Phys Lett 1996, 258: 540.View Article
- Sundqvist B, Edlund U, Jacobsson P, Johnels D, Jun J, Launois P, Moret R, Persson P-A, Soldatov A, Wågberg T: Structural and physical properties of pressure polymerized C 60 . Carbon 1998, 36: 657.View Article
- Chen X, Yamanaka S, Sako K, Inoue Y, Yasukawa M: First single-crystal X-ray structural refinement of the rhombohedral C 60 polymer. Chem Phys Lett 2002, 356: 291.View Article
- Wang G-W, Komatsu K, Murata Y, Shiro M: Synthesis and X-ray structure of dumb-bell-shaped C 120 . Nature 1997, 387: 583.View Article
- Lebedkin S, Gromov A, Giesa S, Gleiter R, Renker B, Rietschel H, Krätschmer W: Raman scattering study of C 120 , a C 60 dimer. Chem Phys Lett 1998, 285: 210.View Article
- Komatsu KK, Wang G-W, Murata Y, Tanaka T, Fujiwara K: Mechanochemical synthesis and characterization of the fullerene dimer C 120 . J Org Chem 1998, 63: 9358.View Article
- Wood JM, Kahr B, Hoke SH, DejarmeII L, Cooks RG, Ben-Amotz D: Oxygen and methylene adducts of C 60 and C 70 . J Am Chem Soc 1991, 113: 5907.View Article
- Zhou P, Rao AM, Wang K-A, Robertson JD, Eloi C, Meier MS, Ren SL, Bi X-X, Eklund PC, Dresselhaus MS: Photo-assisted structural transition and oxygen diffusion in solid C 60 films. Appl Phys Lett 1992, 60: 2871.View Article
- Lebedkin S, Ballenweg S, Gross J, Taylor R, Krätschmer W: Synthesis of C 120 O: A new dimeric  fullerene derivative. Tetrahedron Lett 1995, 36: 4971.View Article
- Penn SG, Costa DA, Balch AL, Lebrilla CB: Analysis of C 60 oxides and C 120 O n (n = 1,2,3) using matrix assisted laser desorption-ionization Fourier transform mass spectrometry. Int J Mass Spectrom Ion Processes 1997, 169/170: 371.View Article
- Gromov A, Lebedkin S, Hull WE, Krätschmer W: Isomers of the dimeric fullerene C 120 O 2 . J Phys Chem A 1998, 102: 4997.View Article
- Krause M, Dunsch L, Seifert G, Fowler PW, Gromov A, Krätschmer W, Gutierez R, Porezag D, Frauenheim T: Vibrational signatures of fullerene oxides. J Chem Soc Faraday Trans 1998, 94: 2287.View Article
- Heymann D, Bachilo SM, Weisman RB, Cataldo F, Fokkens RH, Nibbering NMM, Vis RD, Chibante LPF: C 60 O 3 , a fullerene ozonide: Synthesis and dissociation to C 60 O and O 2 . J Am Chem Soc 2000, 122: 11473.View Article
- Weisman RB, Heymann D, Bachilo SM: Synthesis and characterization of the "missing" oxide of C 60 : [5,6]-open C 60 O. J Am Chem Soc 2001, 123: 9720.View Article
- Resmi MR, Ma S, Caprioli R, Pradeep T: C 120 O n from C 60 Br 24 . Chem Phys Lett 2001, 333: 515.View Article
- Heymann D, Weisman RB: Fullerene oxides and ozonides. CR Chim 2006, 9: 1107.View Article
- Stanley HE: Introduction to phase transition and critical phenomena. Oxford: Oxford University Press; 1971.
- Fukuda T, Ishii K, Kurosu S, Whitby R, Maekawa T: Formation of clusters composed of C60 molecules via self-assembly in critical fluids. Nanotechnology 2007, 18: 145611.View Article
- Somayajulu GR: Estimation procedures for critical constants. J Chem Eng Data 1989, 34: 106.View Article
- Okabe H: Photochemistry of small molecules. New York: Wiley; 1978.
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.