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The discovery of a new form of a pure element is a rather rare occurrence, especially for a common element. Therefore, reports of such discoveries generate an unusual amount of excitement among scientists. An example is the 1985 discovery of a new allotropic form of elemental carbon. The two well-known forms of elemental carbon are graphite and diamond. Both of these contain extended arrays of carbon atoms. In the new form, the carbon atoms are arranged in relatively small clusters of atoms.


Theoretical predictions of buckyball molecules appeared in the late 1960s early 1970s,but they went largely unnoticed. In the early 1970s, the chemistry of unsaturated carbon configurations was studied by a group at the University of Sussex, led by Harry Kroto and David Walton. In the 1980s a technique was developed by Richard Smalley and Bob Curl at Rice University, Texas to isolate these substances. They used laser vaporization of a suitable target to produce clusters of atoms. Kroto realized that by using a graphite target any carbon chains formed could be studied.

Harold Kroto

Richard Smalley

CAS number PubChem ChemSpider ChEBI Beilstein Reference Jmol-3D images [show]

IUPAC name[hide] (C60-Ih)[5,6]fullerene Other names[hide] Buckyball; Fullerene-C60; [60]fullerene Identifiers 99685-96-8 123591 110185 CHEBI:33128 5901022 Image 1 SMILES

[show] Molecular formula Molar mass Appearance Density Melting point Solubility in water Crystal structure Space group Lattice constant Properties C60 1 720.64 g mol Dark needle-like crystals 3 1.65 g/cm [1] sublimates at ~600 C insoluble in water Structure Face-centered cubic,cF1924 Fm3m, No. 225 a = 0.14154 nm


Diamond Crystal Structure density (g cm-3) Lattice constant (A) cubic 3.30 3.513 C-C length (A) C=C length 1.54 Graphite hex. 2.27 a=2.456 b=6.696 1.42 0.0 C60 fcc 1.65 14.15 1.455 1.391 9.08

Standard heats of 0.4 formation (k cal mol-1) bulk modulus (G Pa) melting point (K) index of refraction conductivity resistivity (ohm m) naturally occuring deposit 1200 3700 2.42 insulator 1 x 10E18 kimberlite

207 3800 conductor 1.37 x 10E-5 pegmatite

18(174) sublm. 800 2.2 (600nm) semi conductor 1 x 10E14 (room temp) shungite

Further properties of Buckminsterfullerene

C - C length (gas phase) C=C Cage Diameter C60 - C60 nearest approach Ionisation Potentials C60 to C60+ C60+ to C60 2+ C602+ to C60 3+ C60 3+ to C60 4+ Electron affinity Band Gap relative permitivity absorption coefficients (thin film) 7.6 0.2 eV 12.25 0.5 eV 17.0 0.7 eV 21.7 eV by extrapolation 2.6 eV 1.8 eV 4.4 0.2 6.07 x 10E5 cm-1 @ 220 nm 1.21 x 10E5 cm-1 @ 442 nm 1.458 1.410 7.11 3.1

Solubility (at 303 K) carbon tetrechloride benzene toluene carbon disulphide hexane 0.45 mg ml-1 1.44 mg ml-1 2.15 mg ml-1 5.16 mg ml-1 0.04 mg ml-1

The serendipitous discovery of a third allotropic form in 1985, uncovered a fundamentally different structure of closed carbon cages, which were to become known as fullerenes. This new family of non-planar carbon compounds has generated immense interest within the scientific community in such a short period of time, with thousands of papers published about fullerenes and fullerene-based materials to date.In the early 1970's, the chemistry of unsaturated carbon configurations was studied by a group at the University of Sussex, led by Harry Kroto and David Walton. They developed methods for synthesising long chain polyynes, whose vibration-rotation dynamics were studied by microwave spectroscopy. They then used these observations for molecular radioastronomy. From 1975-78 they studied the longchained polyynylcyanides, HC5N, HC7N and HC9N. These molecules were detected in the cloud material of the interstellar medium by radioastronomy. These molecules turned out to be produced by red giant stars.

In the 1980's a technique was developed by Richard Smalley and Bob Curl at Rice University, Texas. They used laser vaporisation of a suitable target to produce clusters of atoms. Kroto realised that by using a graphite target, that the cluster apparatus would be ideal to probe the formation of carbon chains, and so planned a collaboration between his group at Sussex and the one at Rice. The Sussex/Rice experiment took place in September 1985. The technique probed the carbon plasma produced by the laser vaporisation by time-of-flight mass spectrometry. The experiments confirmed that large carbon chain/clusters were being formed. During the experiments it was noted that the peak for the C60 molecule (and to a lesser extent C70) behaved unusually and formed under all conditions as well as exhibiting great stability. The experimental evidence, a strong peak at 720 amu (atomic mass units), indicated that a carbon molecule with sixty carbon atoms was forming, but provided little structural information. The research group concluded after reactivity experiments, that the most likely structure was a spheroidal molecule. Kroto mentioned Fuller's geodesic dome structures, which contained pentagons as well as hexagons. The idea was quickly rationalised as the basis of an icosohedral symmetry closed cage structure. The geodesic and electronic bonding factors in the structure accounted for the stability of the molecule, and it was named after Buckminster Fuller.

In graphite, the carbon atoms are arranged in sheets with the bonds between the atoms forming hexagons, something like chicken wire. The sheets are only weakly bonded to each other, so they slide past one another, giving graphite a slippery feel and making it a good lubricant. Graphite is also used extensively in studies of the surface effects of energy in the form of light, heat, and electric current. When graphite is subjected to large bursts of energy of these sorts, portions of the top sheet of carbon atoms are ripped out. The ejected portions are studied to learn how the energy interacts with a solid surface. In the early 1980s, Harold W. Kroto of the University of Sussex in England was using microwave spectroscopy to analyze the composition of carbon-rich stars. The analysis indicated that the atmosphere of these stars contained cyanopolyynes, which are composed of chains of alternating carbon and nitrogen atoms. Prof. Kroto wanted to study how these chains could be formed. He contacted Robert F. Curl and Richard E. Smalley at Rice University in Texas because they had been using microwave spectroscopy to analyze clusters of metals formed in Prof. Smalleys lab. Prof. Smalley had an apparatus that could vaporize nearly any material into a plasma. In 1985, Kroto joined Curl and Smalley in Smalleys lab to study the products of carbon vaporization. They fired a high-energy laser beam at a graphite surface and used a stream of helium gas to carry the fragments into a mass spectrometer. The mass spectrometer revealed the masses of the fragments of graphite ejected from the surface. These fragments varied from several atoms up to about 190 atoms. The distribution of fragments depended on the pressure of helium in the carrier stream. As the pressure increased from several torr to about 1 atm, the distribution of fragments changed, and the fragment containing sixty carbon atoms became by far the dominant one. Because the laser pulse and graphite surface had not changed, they reasoned that the fragments that broke off were not changing, but instead that the way these fragments interacted on their way into the mass spectrometer changed. At higher helium pressures, the fragments would be jostled together more than at lower pressures. This jostling leads to the formation of the most stable form of small carbon atom cluster, namely C60.

What is Buckminsterfullerene? In 1985 a new allotrope of carbon (C60) was discovered. Sixty carbon atoms form the shape of a ball like a football with a carbon atom at each corner of the 20 hexagons and 12 pentagons. Each carbon atom (shown below as a circle) has three bonds.
The size of the molecule is almost exactly 1nm in diameter. The ratio of the size of an ordinary soccer ball to the planet Earth is the same as the ratio of the size of a C60 molecule to a soccer ball. These are not called giant molecules because there are only sixty atoms. A large number of these molecules can fit together to form a transparent yellow solid called fullerite.

This form of carbon was named after the American architect Buckminster Fuller, who was famous for designing a large geodesic dome which looked similar (sort of) to the molecular structure of C60. Many other balls of carbon called fullerenes, have since been made, including C70, C76, and C84. These molecules have become known as "buckyballs". Fullerenes are used as catalysts and lubricants. They are also used in nanotubes for strengthening materials (for eaxample sports equipment) and are sometimes used as a way of delivering drugs into the body

Kroto, Smalley, and Curl wondered how the atoms in this cluster were arranged to make it more stable than other clusters. They believed that its stability came from an arrangement in which all bonding capacity of the atoms is satisfied. In a small fragment of carbon-atom sheet ejected from a graphite surface, the atoms around the edge of the sheet would not be fully bonded. If, however, the sheet were to form into a ball so the edges would meet, the bonding capacity of all atoms would be satisfied. In thinking of how the atoms are arranged in this ball, the scientists considered the geodesic domes designed by the architectengineer, R. Buckminster Fuller. These domes led them to suspect a structure of interlocking hexagons and pentagons, identical to those of a soccer ball. Because this idea was inspired by the geodesic dome, they named this C60 allotrope of carbon buckminsterfullerene.

The amounts of buckminsterfullerene (buckyballs, for short) prepared by laser were extremely small. The evidence for the structure would remain sketchy until C60 could be prepared in larger quantities. Such a preparation was discovered in 1990. In this method, a water-cooled cylinder contains a sharp graphite rod touching a graphite disk. The cylinder is evacuated to a pressure of 1 10-5 torr, and a current of 100 to 200 ampere is passed between the rod and the disk. This produces a soot that deposits on the walls of the cylinder. The soot is washed with toluene, producing a red-brown solution. When this solution is evaporated, it leaves a residue with a mass of about 10% of the original soot and containing more than 85% C60. With this method, about 1 gram of C60 can be produced in a day. A whole new chemistry has developed in which fullerene molecules are manipulated to form compounds. Because the C60 sphere is hollow, other atoms can be trapped within it. When a graphite sheet soaked in LaCl3 solution is subjected to vaporization-condensation experiments, a substance with formula LaC60 is formed. When other metal salts are used, the ball of carbon atoms can be shrunken with laser pulses to fit the metal ion within. In this way, CsC48 and KC44 were formed. Other experiments have produced new materials with C60. For example, C60 doped with potassium is a superconductor below 18 Kelvin. In the C60 structure, other atoms have been substituted for the carbon atoms, producing derivatives such as C59N and C57B3. C60 has also been used to produce three-dimensional polymers. In addition, tubes of carbon atoms called nanotubes have also been made. In 1996, Harold Kroto, Richard Smalley, and Robert Curl shared the Nobel Prize in Chemistry for their discovery of buckminsterfullerene.

Beam-experiments conducted between 1985-90 provided more evidence for the stability of C60 as well as supporting the closed cage structural theory and predicting some of the bulk properties such a molecule would have. Around this time, intense theoretical group theory activity also predicted that C60 should have only four IR active vibrational bands, on account of its icosohedral symmetry.In 1989, the Heidelberg/Tuscon group, led by physicists Wolfgang Krtschmer and Donald Huffman had observed unusual IR and UV features in thin carbon films produced by arcprocessed graphite rods. Among other features, the IR spectra showed four discrete bands in close agreement to those proposed for C60. A paper published by the group in 1990 followed on from their thin film experiments, and detailed the extraction of a benzene soluble material from the arcprocessed graphite. This extract was found to crystallise and X-ray analysis consistent with arrays of spherical C60 molecules, approximately 7 in diameter. The C60 molecule has two bond lengths - the 6:6 ring bonds can be considered "double bonds" and are shorter than the 6:5 bonds - see below - the "shorter bonds" are highlighted for clarity:

In 1990, W. Krtchmer and D. R. Huffman's developed a simple and efficient method of producing fullerenes in gram and even kilogram amounts which boosted the fullerene research. In this technique, carbon soot is produced from two high-purity graphite electrodes by igniting an arc discharge between them in an inert atmosphere (helium gas). Alternatively, soot is produced by laser ablation of graphite or pyrolysis of aromatic hydrocarbons. Fullerenes are extracted from the soot using a multistep procedure. First, the soot is dissolved in appropriate organic solvents. This step yields a solution containing up to 75% of C60, as well as other fullerenes. These fractions are separated using chromatography.[12]

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^ Buckminsterfullerene and Buckyballs Definition, Discovery, Structure, Production, Properties and A. July 15, 2006 ^ Katz, 374 ^ Beck, Mihly T.; Mndi, Gza (1997). "Solubility of C60". Fullerenes, Nanotubes and Carbon Nanostructures 5 (2): 291.doi:10.1080/15363839708011993. ^ Bezmel'nitsyn, V.N.; Eletskii, A.V.; Okun', M.V. (1998). "Fullerenes in solutions". Physics-Uspekhi 41 (11): 1091. Bibcode1998PhyU...41.1091B. doi:10.1070/PU1998v041n11ABEH000502. ^ Ruoff, R. S.; Tse, Doris S.; Malhotra, Ripudaman; Lorents, Donald C. (1993). "Solubility of fullerene (C60) in a variety of solvents". Journal of Physical Chemistry 97 (13): 3379. doi:10.1021/j100115a049. ^ M. S. Dresselhaus; G. Dresselhaus; P. C. Eklund (20 February 1996). Science of fullerenes and carbon nanotubes. Academic Press. pp. 437. ISBN 978-0-12-221820-0. Retrieved 26 December 2011. ^ Talyzin, A.V. (1997). "Phase Transition C60C60*4C6H6in Liquid Benzene". Journal of Physical Chemistry B 101 (47): 9679.doi:10.1021/jp9720303. ^ Talyzin, A.V.; Engstrm, I. (1998). "C70 in Benzene, Hexane, and Toluene Solutions". Journal of Physical Chemistry B 102 (34): 6477.doi:10.1021/jp9815255. ^ a b Katz, 372 ^ Katz, 361 ^ Katz, 379 ^ Kaz, 381 ^

Haddon, R. C.; Hebard, A. F.; Rosseinsky, M. J.; Murphy, D. W.; Duclos, S. J.; Lyons, K. B.; Miller, B.; Rosamilia, J. M. et al (1991). "Conducting films of C60 and C70 by alkali-metal doping". Nature 350 (6316): 320. Bibcode 1991Natur.350..320H. doi:10.1038/350320a0. ^ a b Gunnarsson, O. (1997). "Superconductivity in fullerides". Reviews of Modern Physics 69 (2): 575. arXiv:condmat/9611150. Bibcode1997RvMP...69..575G. doi:10.1103/RevModPhys.69.575. ^ Hebard, A. F.; Rosseinsky, M. J.; Haddon, R. C.; Murphy, D. W.; Glarum, S. H.; Palstra, T. T. M.; Ramirez, A. P.; Kortan, A. R. (1991). "Superconductivity at 18 K in potassium-doped C60". Nature 350 (6319): 600. Bibcode 1991Natur.350..600H. doi:10.1038/350600a0. ^ "Superconductivity at 28 K in Rb_{x}C_{60}". Physical Review Letters 66: 2830. 1991. Bibcode 1991PhRvL..66.2830R.doi:10.1103/PhysRevLett.66.2830. ^ Chen, C.-C.; Kelty, S. P.; Lieber, C. M. (1991). "(RbxK1-x)3C60 Superconductors: Formation of a Continuous Series of Solid Solutions".Science 253 (5022): 8868. Bibcode 1991Sci...253..886C. doi:10.1126/science.253.5022.886. PMID 17751824. ^ Zhou, O.; Zhu, Q.; Fischer, J. E.; Coustel, N.; Vaughan, G. B. M.; Heiney, P. A.; McCauley, J. P.; Smith, A. B. (1992). "Compressibility of M3C60 Fullerene Superconductors: Relation Between Tc and Lattice Parameter". Science 255 (5046): 833 5. Bibcode 1992Sci...255..833Z.doi:10.1126/science.255.5046.833. PMID 17756430. ^ "Pressure dependence of superconductivity in the Na_{2}Rb_{0.5}Cs_{0.5}C_{60} fulleride". Physical Review B 59: 4439. 1999. Bibcode1999PhRvB..59.4439B. doi:10.1103/PhysRevB.59.4439. ^ a b Ganin, Alexey Y.; Takabayashi, Yasuhiro; Khimyak, Yaroslav Z.; Margadonna, Serena; Tamai, Anna; Rosseinsky, Matthew J.; Prassides, Kosmas (2008). "Bulk superconductivity at 38 K in a molecular system". Nature 7 (5): 367 71. Bibcode 2008NatMa...7..367G.doi:10.1038/nmat2179. PMID 18425134. ^ Tanigaki, K.; Ebbesen, T. W.; Saito, S.; Mizuki, J.; Tsai, J. S.; Kubo, Y.; Kuroshima, S. (1991). "Superconductivity at 33 K in CsxRbyC60". Nature352 (6332): 222223. Bibcode 1991Natur.352..222T. doi:10.1038/352222a0. ^ a b Iwasa, Y; Takenobu, T (2003). "Superconductivity, Mott Hubbard states, and molecular orbital order in intercalated fullerides". Journal of Physics: Condensed Matter 15 (13): R495. Bibcode 2003JPCM...15R.495I. doi:10.1088/0953-8984/15/13/202. ^ "Electronic structure of crystalline K_{6}C_{60}". Physical Review Letters 67: 1610. 1991. Bibcode 1991PhRvL..67.1610E.doi:10.1103/PhysRevLett.67.1610.

^ "Electronic structure of superconducting Ba_{6}C_{60}". Physical Review B 47: 14657. 1993. arXiv:condmat/9301006. Bibcode1993PhRvB..4714657E. doi:10.1103/PhysRevB.47.14657. ^ "Strong Superconductivity with Local Jahn-Teller Phonons in C_{60} Solids". Physical Review Letters 90: 167006. 2003. Bibcode2003PhRvL..90p7006H. doi:10.1103/PhysRevLett.90.167006. PMID 1 2731998. ^ Capone, M.; Fabrizio, M; Castellani, C; Tosatti, E (2002). "Strongly Correlated Superconductivity". Science 296 (5577): 23646. arXiv:condmat/0207058. Bibcode 2002Sci...296.2364C. doi:10.1126/science.1071122. PMID 120 89436. ^ Fullerene Hydration ^ Andrievsky, G; Klochkov, V.K.; Bordyuh, A.B.; Dovbeshko, G.I. (2002). "Comparative analysis of two aqueous-colloidal solutions of C60 fullerene with help of FTIR reflectance and UVVis spectroscopy". Chemical Physics Letters 364: 8. Bibcode 2002CPL...364....8A.doi:10.1016/S0009-2614(02)01305-2. ^ Andrievsky, G.; Klochkov, V.; Derevyanchenko, L. (2005). "Is the C 60 Fullerene Molecule Toxic?!". Fullerenes, Nanotubes, and Carbon Nanostructures 13 (4): 363. doi:10.1080/15363830500237267. ^ Andrievsky, GV; Bruskov, VI; Tykhomyrov, AA; Gudkov, SV (2009). "Peculiarities of the antioxidant and radioprotective effects of hydrated C60 fullerene nanostuctures in vitro and in vivo". Free radical biology & medicine 47 (6): 786 93. doi:10.1016/j.freeradbiomed.2009.06.016.PMID 19539750. ^ Katz, 385 ff.

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Buckminster Fuller's Dome - Expo '67 Montreal Courtesy of B. Eggen (Univ. of Sussex)

It's stronger than it looks. It superconducts (conducts electricity really well) when you fiddle with it enough.

It insulates (doesn't conduct at all) on that same token. It conducts like an ordinary metal. It even semiconducts (a bit like silicon) under the right conditions. You can make it switch between all these states by playing with it. Some pharmaceutical companies are developing products containing C60 to make you look younger. However, C60 has not been tested properly for toxicity yet. Some people have made transistors out of it. It's hollow, so you can wrap it around single atoms and trap them 'in a cage'. Somebody went and made an amplifier using a single molecule of it. It's optically active, meaning that if you put it in front of a light source, you can use it to switch the light on and off, and things like that. It can be really useful if you are a telecommunications engineer. Bioactivity is another application, C60 can be made to fiddle with DNA and some sugars. Because the molecule is a tiny strong sphere, it can be used as a microscopic ball bearing for very small machines. There are more applications and a great many academic papers have been published concerning C60, but the list could become long and boring and it's growing daily. It could also be the first step into nanotechnology. So there you have it: a molecule so new and weird, they don't even know what to do with it yet.

13 C NMR

A C60
B C70

SPECTROSCOPIC DATA Rotational constant 0.0028 cm-1 IR active bands - four T1u

solid* (cm-1) 1429.0 1182.5 576.5 527.0

Gas phase 1406.9 1169.1 570.3 527.0

Ar matrix 1431.9 1184.8 579.3 530.0

(micro m)

6.998 8.456 17.35 18.87

7.108 8.554 17.53 18.98

6.984 8.440 17.26 18.87

UV and visible bands (hexane)

a broad weak band also exists between 440 - 670 nm. Also detected are bands assigned to the ions; C60+ at 973 nm and C60- at 1068 nm. nm 211.0 227.4 256.6 328.4 377.0 404.0 cm-1 47393 43975 38971 30451 26525 24754 log emax 5.20 4.95 5.24 4.72 3.79 3.47 eV 5.88 5.46 4.83 3.78 3.29 3.07

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