- "C60" and "C-60" redirect here. For other uses, see C60 (disambiguation).
Fullerenes are a family of carbon allotropes, molecules composed entirely of carbon, in the form of a hollow sphere, ellipsoid, tube, or plane . Spherical fullerenes are also called buckyballs, and cylindrical ones are called carbon nanotubes or buckytubes. Graphene is an example of a planar fullerene sheet. Fullerenes are similar in structure to graphite, which is composed of a sheet of linked hexagonal rings, but may also contain pentagonal (or sometimes heptagonal) rings that would prevent a sheet from being planar.
- 1 Prediction and discovery
- 2 Variations
- 3 Buckyballs
- 4 Buckytubes
- 5 Properties
- 6 Examples of fullerenes in Popular culture
- 7 Fullerite (solid state)
- 8 See also
- 9 References
- 10 Further reading
- 11 External links
Prediction and discovery
In molecular beam experiments, discrete peaks were observed corresponding to molecules with the exact mass of sixty or seventy or more carbon atoms. In 1985, Harold Kroto (then of the University of Sussex, now of Florida State University), James R. Heath, Sean O'Brien, Robert Curl and Richard Smalley, from Rice University, discovered C60, and shortly thereafter came to discover the fullerenes. Kroto, Curl, and Smalley were awarded the 1996 Nobel Prize in Chemistry for their roles in the discovery of this class of compounds. C60 and other fullerenes were later noticed occurring outside the laboratory (e.g., in normal candle soot). By 1991, it was relatively easy to produce gram-sized samples of fullerene powder using the techniques of Donald Huffman and Wolfgang Krätschmer. Fullerene purification remains a challenge to chemists and to a large extent determines fullerene prices. So-called endohedral fullerenes have ions or small molecules incorporated inside the cage atoms. Fullerene is an unusual reactant in many organic reactions such as the Bingel reaction discovered in 1993.
Minute quantities of the Buckminsterfullerenes, in the form of C60, C70, C76, and C84 molecules, are produced in nature, hidden in soot and formed by lightning discharges in the atmosphere. Recently, Buckminsterfullerenes were found in a family of minerals known as Shungites in Karelia, Russia.
The existence of C60 was predicted in 1970 by Eiji Osawa of Toyohashi University of Technology. He noticed that the structure of a corannulene molecule was a subset of a soccer-ball shape, and he made the hypothesis that a full ball shape could also exist. His idea was reported in Japanese magazines, but did not reach Europe or America.
Buckminsterfullerene (C60) was named after Richard Buckminster Fuller, a noted architect who popularized the geodesic dome. Since buckminsterfullerenes have a similar shape to that sort of dome, the name was thought to be appropriate. As the discovery of the fullerene family came after buckminsterfullerene, the name was shortened to illustrate that the latter is a type of the former.
For illustrations of geodesic dome structures, see Montreal Biosphere, Eden Project, Missouri Botanical Garden, Science World at Telus World of Science, Mitchell Park Horticultural Conservatory, Gold Dome, Tacoma Dome, Reunion Tower, and Spaceship Earth (Disney).
Since the discovery of fullerenes in 1985, structural variations on fullerenes have evolved well beyond the individual clusters themselves. Examples include:
- buckyball clusters: smallest member is C
20 and the most common is C
- nanotubes: hollow tubes of very small dimensions, having single or multiple walls; potential applications in electronics industry;
- megatubes: larger in diameter than nanotubes and prepared with walls of different thickness; potentially used for the transport of a variety of molecules of different sizes;
- polymers: chain, two-dimensional and three-dimensional polymers are formed under high pressure high temperature conditions
- nano"onions": spherical particles based on multiple carbon layers surrounding a buckyball core; proposed for lubricants;
- linked "ball-and-chain" dimers: two buckyballs linked by a carbon chain;
- fullerene rings
Buckminsterfullerene (IUPAC name (C60-Ih)[5,6]fullerene) is the smallest fullerene molecule in which no two pentagons share an edge (which can be destabilizing; see pentalene). It is also the most common in terms of natural occurrence, as it can often be found in soot.
The structure of C60 is a truncated (T = 3) icosahedron, which resembles a soccer ball of the type made of twenty hexagons and twelve pentagons, with a carbon atom at the vertices of each polygon and a bond along each polygon edge.
The C60 molecule has two bond lengths. The 6:6 ring bonds (between two hexagons) can be considered "double bonds" and are shorter than the 6:5 bonds (between a hexagon and a pentagon).
A new type of buckyball utilizing boron atoms instead of the usual carbon has been predicted and described by researchers at Rice University. The B-80 structure is predicted to be more stable than the C-60 buckyball. One reason for this given by the researchers is that the B-80 is actually more like the original geodesic dome structure popularized by Buckminster Fuller which utilizes triangles rather than hexagons.
Variations of buckyballs
In mathematical terms, the structure of a fullerene is a trivalent convex polyhedron with pentagonal and hexagonal faces. In graph theory, the term fullerene refers to any 3-regular, planar graph with all faces of size 5 or 6 (including the external face). It follows from Euler's polyhedron formula, |V|-|E|+|F| = 2, (where |V|, |E|, |F| indicate the number of vertices, edges, and faces), that there are exactly 12 pentagons in a fullerene and |V|/2-10 hexagons.
The smallest fullerene is the dodecahedron--the unique C20. There are no fullerenes with 22 vertices. The number of fullerenes C2n grows with increasing n = 12,13,14..., roughly in proportion to n9. For instance, there are 1812 non-isomorphic fullerenes C60. Note that only one form of C60, the buckminsterfullerene alias truncated icosahedron, has no pair of adjacent pentagons (the smallest such fullerene). To further illustrate the growth, there are 214,127,713 non-isomorphic fullerenes C200, 15,655,672 of which have no adjacent pentagons.
TRIMETASPHERE® carbon nanomaterials were discovered by researchers at Virginia Tech and licensed exclusively to Luna Innovations. This class of novel molecules comprises 80 carbon atoms (C80) forming a sphere which encloses a complex of three metal atoms and one nitrogen atom. These fullerenes encapsulate metals which puts them in the subset referred to as metallofullerenes. TRIMETASPHERES have the potential for use in diagnostics (as safe imaging agents), therapeutics and in organic solar cells.
Nanotubes are cylindrical fullerenes. These tubes of carbon are usually only a few nanometres wide, but they can range from less than a micrometer to several millimeters in length. They often have closed ends, but can be open-ended as well. There are also cases in which the tube reduces in diameter before closing off. Their unique molecular structure results in extraordinary macroscopic properties, including high tensile strength, high electrical conductivity, high ductility, high resistance to heat, and relative chemical inactivity (as it is cylindrical and "planar"—that is, it has no "exposed" atoms that can be easily displaced). One proposed use of carbon nanotubes is in paper batteries, developed in 2007 by researchers at Rensselaer Polytechnic Institute.
Nanobuds have been obtained by adding Buckminsterfullerenes to carbon nanotubes.
For the past decade, the chemical and physical properties of fullerenes have been a hot topic in the field of research and development, and are likely to continue to be for a long time. Popular Science has published articles about the possible uses of fullerenes in armor. In April 2003, fullerenes were under study for potential medicinal use: binding specific antibiotics to the structure to target resistant bacteria and even target certain cancer cells such as melanoma. The October 2005 issue of Chemistry and Biology contains an article describing the use of fullerenes as light-activated antimicrobial agents.
A common method used to produce fullerenes is to send a large current between two nearby graphite electrodes in an inert atmosphere. The resulting carbon plasma arc between the electrodes cools into sooty residue from which many fullerenes can be isolated.
There are many calculations that have been done using ab-initio Quantum Methods applied to fullerenes. By DFT and TD-DFT methods one can obtain IR, Raman and UV spectra. Results of such calculations can be compared with experimental results.
Researchers have been able to increase the reactivity of fullerenes by attaching active groups to their surfaces. Buckminsterfullerene does not exhibit "superaromaticity": that is, the electrons in the hexagonal rings do not delocalize over the whole molecule.
A spherical fullerene of n carbon atoms has n pi-bonding electrons. These should try to delocalize over the whole molecule. The quantum mechanics of such an arrangement should be like one shell only of the well-known quantum mechanical structure of a single atom, with a stable filled shell for n = 2, 8, 18, 32, 50, 72, 98, 128, etc.; i.e. twice a perfect square; but this series does not include 60. As a result, C60 in water tends to pick up two more electrons and become an anion. The nC60 described below may be the result of C60's trying to form a loose metallic bonding.
Fullerenes are stable, but not totally unreactive. The sp2-hybridized carbon atoms, which are at their energy minimum in planar graphite, must be bent to form the closed sphere or tube, which produces angle strain. The characteristic reaction of fullerenes is electrophilic addition at 6,6-double bonds, which reduces angle strain by changing sp2-hybridized carbons into sp3-hybridized ones. The change in hybridized orbitals causes the bond angles to decrease from about 120 degrees in the sp2 orbitals to about 109.5 degrees in the sp3 orbitals. This decrease in bond angles allows for the bonds to bend less when closing the sphere or tube, and thus, the molecule becomes more stable.
Other atoms can be trapped inside fullerenes to form inclusion compounds known as endohedral fullerenes. An unusual example is the egg shaped fullerene Tb3N@C84, which violates the isolated pentagon rule. Recent evidence for a meteor impact at the end of the Permian period was found by analysing noble gases so preserved. Metallofullerene-based inoculates using the rhonditic steel process are beginning production as one of the first commercially-viable uses of buckyballs.
Fullerenes are sparingly soluble in many solvents. Common solvents for the fullerenes include aromatics, such as toluene, and others like carbon disulfide. Solutions of pure Buckminsterfullerene have a deep purple color. Solutions of C70 are a reddish brown. The higher fullerenes C76 to C84 have a variety of colors. C76 has two optical forms, while other higher fullerenes have several structural isomers. Fullerenes are the only known allotrope of carbon that can be dissolved in common solvents at room temperature.
Some fullerene structures are not soluble because they have a small band gap between the ground and excited states. These include the small fullerenes C28, C36 and C50. The C72 structure is also in this class, but the endohedral version with a trapped lanthanide-group atom is soluble due to the interaction of the metal atom and the electronic states of the fullerene. Researchers had originally been puzzled by C72 being absent in fullerene plasma-generated soot extract, but found in endohedral samples. Small band gap fullerenes are highly reactive and bind to other fullerenes or to soot particles.
Solvents that are able to dissolve buckminsterfullerene (C60) are listed below in order from highest solubility. The value in parentheses is the approximate saturated concentration.
- 1-chloronaphthalene (51 mg/mL)
- 1-methylnaphthalene (33 mg/mL)
- 1,2-dichlorobenzene (24 mg/mL)
- 1,2,4-trimethylbenzene (18 mg/mL)
- tetrahydronaphthalene (16 mg/mL)
- carbon disulfide (8 mg/mL)
- 1,2,3-tribromopropane (8 mg/mL)
- bromoform (5 mg/mL)
- toluene (3 mg/ml)
- benzene (1.5 mg/ml)
- cyclohexane (1.2 mg/ml)
- carbon tetrachloride (0.4 mg/ml)
- chloroform (0.25 mg/ml)
- n-hexane (0.046 mg/ml)
- tetrahydrofuran (0.006 mg/ml)
- acetonitrile (0.004 mg/ml)
- methanol (0.00004 mg/ml)
- water (1.3x10-11 mg/mL)
Solubility of C60 in some solvents shows unusual behaviour due to existence of solvate phases (analogues of crystallohydrates). For example, solubility of C60 in benzene solution shows maximum at about 313 K. Crystallization from benzene solution at temperatures below maximum results in formation of triclinic solid solvate with four benzene molecules C60•4C6H6 which is rather unstable in air. Out of solution, this structure decomposes into usual fcc C60 in few minutes' time. At temperatures above solubility maximum the solvate is not stable even when immersed in saturated solution and melts with formation of fcc C60. Crystallization at temperatures above the solubility maximum results in formation of pure fcc C60. Large millimetre size crystals of C60 and C70 can be grown from solution both for solvates and for pure fullerenes.
In 1999, researchers from the University of Vienna demonstrated that the wave-particle duality applied to molecules such as fullerene. One of the co-authors of this research, Julian Voss-Andreae, became an artist and has since created several sculptures symbolizing wave-particle duality in Buckminsterfullerenes.
Science writer Marcus Chown stated on the CBC radio show "Quirks And Quarks" in May 2006 that scientists are trying to make buckyballs exhibit the quantum behavior of existing in two places at once (quantum superposition).
F. Moussa et al. (1996, Fullerene Sci.Technol., 4 ; pp. 21-29 and 1997, Proc. Electrochem. Soc., 5; pp. 332-336) studied the in vivo toxicity of C60 after intra-peritoneal administration of large doses. No evidence of toxicity was found and the mice tolerated a dose of 5000 mg/kg of body weight (BW). Ten years later, T. Mori et al. (2006, Toxicology, 225; pp. 48–54) confirmed the absence of toxicity in rodents for C60 and C70 mixtures after oral administration of a dose of 2000 mg/kg BW and showed no evidence of genotoxic or mutagenic potential in vitro. Recently, many studies have shown fullerenes to be non-toxic, on the contrary, N. Gharbi et al. (2005, Nano Letters, vol.5, No. 12, pp.2578-2585) showed that aqueous C60 suspensions not only have no acute or subacute toxicity in rodents but they also protect their livers in a dose-dependent manner against free-radical damage. A comprehensive and recent review of work on fullerene toxicity is available in "Toxicity Studies of Fullerenes and Derivatives", a chapter from the book Bio-applications of Nanoparticles (Kolosnjaj J. et al. Toxicity studies of fullerenes and derivatives. Bioapplications of nanoparticles. Eds WC Chan, Landes Biosciences, Toronto, On, CA. 2007, Chap 13, p :168-180). In this work, the authors review the work on fullerene toxicity beginning in the early 1990s to present, and conclude that the evidence gathered since the discovery of fullerenes overwhelmingly suggests that C60 is non-toxic.
Examples of fullerenes in Popular culture
Examples of fullerenes in popular culture are numerous. Fullerenes appeared in fiction well before scientists took serious interest in them. It is the topic of a science fiction book named Decipher written by Stel Pavlou. In New Scientist there used to be a weekly column called "Daedalus" written by David Jones, which contained humorous descriptions of unlikely technologies. In 1966 the columnist included a description of C60 and other forms of graphite. This was meant as pure entertainment. Also in New Scientist magazine, a free book was enclosed entitled, "100 Things to Do Before You Die", one of which was to kick a buckyball. The buckyball is the state molecule of Texas. Bucky Balls were also mentioned in A&E's 2008 remake of The Andromeda Strain, which is based on the Michael Crichton novel of the same name.
Fullerite (solid state)
Fullerites are the solid-state manifestation of fullerenes and related compounds and materials.
Polymerized single walled nanotubes (P-SWNT) are a class of fullerites and are comparable to diamond in terms of hardness. However, due to the way that nanotubes intertwine, P-SWNTs do not have the corresponding crystal lattice that makes it possible to cut diamonds neatly. This same structure results in a less brittle material, as any impact that the structure sustains is spread out throughout the material. Because nanotubes are still very expensive to produce in useful quantities, uses for a material lighter and stronger than steel will have to wait until nanotube production becomes more economically viable.
Ultrahard fullerite, Buckyball
Ultrahard fullerite (C60) is a form of carbon synthesized under high pressure high temperature conditions. It is believed that fullerene molecules are three-dimensionally polymerized in this material.
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- Bucky's brother -- The boron buckyball makes its début Jade Boyd April 2007 eurekalert.orgLink
- Buckminsterfullerene: Molecule of the Month
- V. L. Pushparaj, M. M. Shaijumon, A. Kumar, S. Murugesan, L. Ci, R. Vajtai, R. J. Linhardt, O. Nalamasu and P. M. Ajayan (2007). "Flexible energy storage devices based on nanocomposite paper". Proceedings of the National Academy of Sciences. 104 (34). doi:10.1073/pnas.0706508104. Lay summary – TechNewsWorld (2007-08-14).
- Tegos, G. (2005). "Cationic Fullerenes Are Effective and Selective Antimicrobial Photosensitizers". Chemistry & Biology. 12 (10): 1127–1135. Unknown parameter
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- egg shaped fullerene: Link.
- Becker, Luann (2007-02-23). "Impact Event at the Permian-Triassic Boundary: Evidence from Extraterrestrial Noble Gases in Fullerenes". Science. 291 (5508): 1530–3. doi:10.1126/science.1057243. Retrieved 2007-03-13. Unknown parameter
- Ab initio theoretical predictions of C28, C28H4, C28F4, (Ti at C28)H4, and M at C28 (M = Mg, Al, Si, S, Ca, Sc, Ti, Ge, Zr, and Sn), Guo, Ting; Smalley, Richard E.; Scuseria, Gustavo E., 1993.
- Fullerenes in Solutions, Bezmel'nitsyn, V.N.; Eletskiĭ, A.V.; Okun', M.V., Uspekhi Fizicheskikh Nauk, Russian Academy of Sciences, 41 1998.
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|coauthors=ignored (help); Unknown parameter
- The radio show can be heard at: http://www.cbc.ca/quirks/archives/05-06/jun17.html
- State molecule of Texas: Link
- Diamonds lose 'world's hardest' title
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|Wikimedia Commons has media related to Buckminsterfullerene.|
- Pharmacological Studies on Fullerene (C60), a Novel Carbon Allotrope, and Its Derivatives
- Fullerenes in solution: about anomalous temperature dependence of solubility and solid solvates of fullerenes
- Fullerene and nanotube Gallery
- Properties of C60 fullerene
- Buckyball Workshops by Sir Harry Kroto and the Vega Science Trust
- Center for Nanoscale Science and Technology
- Center for Biological and Environmental Nanotechnology
- Dr. Smalley's brief autobiography
- Dr. Smalley's webpage
- Sir Harry Kroto's webpage
- Interview with James R. Heath, discussing the discovery of C60
- Diffraction and Interference with Fullerenes: Wave-particle duality of C60, University of Vienna
- Fullerene-based architectures for quantum computing in Germany and in Great Britain at the QIP IRC
- Molview from bluerhinos.co.uk See Buckminsterfullerene (C60) in 3D
- Computational Chemistry Wiki
- A Spherical Revelation
- C60 3D-view and pdb-file
- Simple model of Fullerene.
- Story on "Buckyeggs" (UC Davis website)
- Stainless Steel Buckminster Fullerenes
- Rhonditic Steel
- Introduction to fullerites
- Introduction to P-SWNT
- Fullerene Supplier : 
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