1. Fullerene and metal Cluster
AMITY UNIVERSITY
RAJASTHAN
Fullerene and metal Cluster
SUBHRANGSU SEKHAR DEY
M.Sc Applied Chemistry
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2. Fullerene Introduction of Fullerene family (what is?)
Fullerene (discovery, naming)
Types of Fullerene and related structures
Properties
Synthesis (to fabricate)
Potential and current applications
Metal Cluster
Molecular Cluster
Model for the Properties
High Energy Ionization
Types Of Cluster
Gas-phase clusters and fullerenes
Now we will begin to know about the fullerene family. What is fullerene? Different structures of
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3.  What is Fullerene? 
A Fullerene is any molecule composed entirely of carbon, in the form of a hollow sphere, ellipsoid, or tube. Spherical fullerenes are also called buckyballs, and cylindrical ones are called carbon nanotubes or buckytubes.
Buckminster fullerene C60 (left) and carbon nanotubes (right) are two examples of structures in the fullerene family.
C60 in solution
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4. Allotropes of carbon Allotropes :
different structural modifications of an element; the atoms of the element are bonded together in a different manner.
Allotropes of carbon:
Diamond (hardest natural mineral)
Graphite(dry lubricant, graphene)
Amorphous carbon (coal and soot)
Fullerene family (C60, carbon nanotubes etc)
4 common allotropes of carbon are graphene, diamond (where the carbon atoms are bonded together in a tetrahedral lattice arrangement), graphite (where the carbon atoms are bonded together in sheets of a hexagonal lattice), and fullerenes (where the carbon atoms are bonded together in spherical, tubular, or ellipsoidal formations).
Diamond and graphite are two allotropes of carbon: pure forms of the same element that differ in structure.
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5. Fullerene-History
The existence of C60 was predicted by Eiji Osawa of Toyohashi University of Technology in a Japanese magazine in 1970
With mass spectrometry, discrete peaks were observed corresponding to molecules with the exact mass of sixty or seventy or more carbon atoms. In 1985, Harold Kroto etc，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.
Minute quantities of the fullerenes, 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.
Buckminsterfullerene C60
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The Icosahedral Fullerene C540
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6. Discovery of Carbon C60
1985, Robert F. Curl, … discovered a new form of carbon，that 60 or 70 carbon atoms could cluster together to form a cage-like molecule.
The molecular structure resembled the pattern of a soccer ball or the geodesic designs of Buckminster Fullerenes. Thus the name buckyballs or fullerenes.
Since then the discovery has led to new research in polymers, semiconductors, and other various areas.
Nobel Prize to their finders in 1996
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7. Existence in the nature
In 1992, fullerenes were found in a family of minerals known as Shungites in Karelia, Russia.
In 2010, fullerenes (C60) have been discovered in a cloud of cosmic dust surrounding a distant star 6500 light years away. Using NASA's Spitzer infrared telescope the scientists spotted the molecules' unmistakable infrared signature. Sir Harry Kroto, who shared the 1996 Nobel Prize in Chemistry for the discovery of buckyballs commented: "This most exciting breakthrough provides convincing evidence that the buckyball has, as I long suspected, existed since time immemorial in the dark recesses of our galaxy”
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8. Naming--Fullerene
The substance of the Fullerene was named after the American inventor, architects and philosophers Richard Buckminster Fuller (1895 till 1983). As an architect, R.B.Fuller designed the constructions which exist of 5-corners and 6- corners, for example, the American pavilion to the Expo in '67 in Montréal(geodesic dome).
Fullerenes are similar in structure to graphite, which is composed of stacked graphene sheets of linked hexagonal rings; but they may also contain pentagonal (or sometimes heptagonal) rings.
As the discovery of the fullerene family came after buckminsterfullerene, the shortened name 'fullerene' is used to refer to the family of fullerenes. The suffix “ene” indicates that each C atom is covalently bonded to three others (instead of the maximum of four), a situation that classically would correspond to the existence of bonds involving two pairs of electrons (“double bonds”).
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9. After the IUPAC nomenclature the C60 has the following name:
[ ,14.03,12. 04,59.05,10.06, ,55.08,53.09, ,20.013,18.015, ,28.017,25.019, , ,49.027, ,45.032,44.033, ,57.035,43.036, ,41.038,54.039, ,48.042,46]hexaconta- 1,3,5(10),6,8,11,13(18), 14,16,19,21,23,25,27,29(45),30,32(44),33,35(43), 36,38(54),39(51),40(48),41,46,49,52,55,57,59- triacont
hexacosanoic acid [化]二十六(烷)酸,蜡酸, triacontahedron三十面体
IUPAC--International Union of Pure and Applied Chemistry
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10. FULLERENE MOLECULAR MODELS C56-C76
C56 (Td) Model
C58 (C3v)
C56 (Td) Rotating Animation
C60(C2v)
C76 (D2)
C72 (D6d)
C60(C2v)
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11. Different structure buckyballs
C C C C70
Another fairly common fullerene is C70, but fullerenes with 72, 76, 84 and even up to 100 carbon atoms are commonly obtained. 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 are the numbers of vertices, edges, and faces), that there are exactly 12 pentagons in a fullerene and V/2 − 10 hexagons.
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12. Fullerene Family
Fig. 3.1: A schematic representation of the structures of graphite, diamond and fullerenes. While the two-dimensional sheets formed by hexagons are packed one over another in graphite, the diamond structure is three-dimensional. Only two fullerenes are shown. The smaller one is buckminsterfullerene, C60. structure. The double bonds are localized exocyclic to the pentagons giving [5] radialene character to the pentagons and cyclohexa-1,3,5-triene character to the hexagons.
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13. Synthesis(discover) of C60
Fig. 3.2: The experimental set-up used to discover C60. The graphite disk is evaporated with a Nd:YAG laser and the evaporated carbon plasma is cooled by a stream of helium coming from a pulsed valve. The clusters of carbon are produced in the integration cup and are expanded into vacuum. The ions are detected by time of flight mass spectrometry
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14. synthesis and purification of fullerenes
Fig. 3.4: Schematic illustration of the processed involved in the synthesis and purification of fullerenes. Graphite rods are evaporated in an arc, under He atmosphere. The soot collected is extracted with toluene and subjected to chromatography.
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15. Halogenation Reaction of C60
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Halogenation Reaction of C60

16. Properties & Applications
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
use of fullerenes as light-activated antimicrobial agents
C60 in solution
Fullerenes are stable, but not totally unreactive.
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.
Solubility
Fullerenes are sparingly soluble in many solvents
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
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17. Properties & Applications
(Bottom) Mass spectrum of a laser evaporated C60 film showing coalescence of fullerenes. Mass peaks are seen at (C60)n (Ref.64). (Top) Collision of high energy ions on C60 results in the addition of C2s to C60. The mass spectrum here shows the addition of a number of such species (Ref.65). Combined figure originally published in, T. Pradeep, Current Science, 72 (1997) 124.
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18. Properties & Applications
Hydrated Fullerene
Hydrated fullerene C60HyFn is a stable, highly hydrophilic, supra-molecular complex consisting of С60 fullerene molecule enclosed into the first hydrated shell that contains 24 water molecules:
C60HyFn water solution with a C60 concentration of 0.22 mg/mL
Superconductivity
that intercalation of alkali-metal atoms in solid C60 leads to metallic behavior. In 1991, it was revealed that potassium-doped C60 becomes superconducting at 18 K. This was the highest transition temperature for a molecular superconductor. Since then, superconductivity has been reported in fullerene doped with various other alkali metals
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19. Properties & Applications
Normalized DC electrical resistivity ρ（T）of a K3 C60 single crystal. The Tc observed is 19.8K. ρ0 is the resistivity at T=280K.
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20. Metal Cluster
A characteristic of metal atoms bonded to organic ligands, especially CO, is their tendency to covalently bond to other metal atoms, giving rise to metal-metal bonded cluster compounds.
There appears to be no limit to the size of metal clusters. They can contain numbers of metal atoms ranging from 2 or 3 to several dozen. e.g. Ru3(CO)12, Ir4(CO)12, Pt38(CO)44
Metal clusters may contain single, double, triple or quadruple bonds between metal atoms. Metal clusters can encapsulate non-metallic atoms such as C or N (carbide or nitride clusters) in which the non metal may be bonded to 5 or 6 metal atoms, e.g. [Fe6C(CO)16]2-.
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21. Metal Cluster
They may or may not contain bridging CO ligands (e.g. m2-CO, m3-CO). As negative charge accumulates in series of isoelectronic clusters, more carbonyls are found to be bridging. Bridging tendency decreases down a group.
The metallic skeleton is generally derived from polyhedra that may resemble bulk metals in structure. e.g. [Rh13(CO)24H3]2- and Pt3S(CO)44 resemble hexagonal close packed and body centered cubic metallic lattices, respectively, with "rounded surfaces".
Clusters can exhibit properties characteristic of heterogeneous catalytic metal surfaces
p-acid ligand clusters show structural analogies to boron clusters
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22. Molecular Cluster
Atomic and molecular clusters are aggregates of 5-105
atomic or molecular units. They are classified according
to the forces holding them together:
Van der Waals clusters - attraction between induced
electric dipoles and repulsion between electron cores
of closed electronic configurations
Metallic clusters - long range valence electron sharing
(over many successive adjacent atoms) and partially
Directional
Ionic clusters - valence electrons are almost entirely
transferred among closest neighbors to yield 2 net,
equal but opposite, electric charge distributions that
mutually attract.
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23. Subhrangsu
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24. Model for the Properties
A number of models have been introduced to explain and predict the properties of metal clusters.1. The Liquid Drop Model, failed LDM require a Quantum Mechanical model with discrete electronic states then come JELLIUM MODEL Mass spectra obtained by Knight and co-workers ( ), for alkali metal clusters, showed a number of peaks with high relative intensities  Magic Numbers
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25. High Energy Ionization
Magic numbers due to stability of cationic clusters (MX+): N* = 9, 21, 41, 59 …
Note: Na8, Na9+ both have 8 electrons. MN e
MN+
+ e
high E h
highly electronically
excited
MX+
+ (N-X) M
evaporation
of M atoms
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26. Types Of Cluster 1.Atomic clusters 2. Molecular clusters
3. Transition metal carbonyl clusters Exp.Ni(CO)4 and Fe(CO)5 ,
Fe2(CO)9 and Fe3(CO)12 and Rh13(CO)24H3]₂-(made from Pt)
4. Transition metal organic carbon. Exp:Methyl carbyne ligand (CCH3) bonded to three cobalt atoms: [Co3(CCH3)(CO)9].[3]
(organometallic) clusters
5. Transition metal halide clusters Exp:F. Albert Cotton established that “ReCl3" in fact features subunits of the cluster Re3Cl9,
6. Boron hydrides
7. Fe-S clusters in biology
8. Zintl clusters
9. Metalloid clusters
10. Intermetalloid clusters
And also used as Catalyst.(ficher Topch catalysis)
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27. Gas-phase clusters and fullerenes
Unstable clusters can also be observed in the gas-phase by means of mass spectrometry even though they may be thermodynamically unstable and aggregate easily upon condensation. Such naked clusters, i.e. those that are not stabilized by ligands, are often produced by laser induced evaporation – or ablation - of a bulk metal or metalcontaining compound. Typically, this approach produces a broad distribution of size distributions. Their electronic structures can be interrogated by techniques such as photoelectron spectroscopy, while infrared multiphoton dissociation spectroscopy is more probing the clusters
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28. Properties
Their properties (Reactivity, Ionization potential, HOMO–LUMO-gap) often show a pronounced size dependence. Examples of such clusters are certain aluminium clusters as superatoms and certain gold clusters.Certain metal clusters are considered to exhibit metal aromaticity. In some cases, the results of laser ablation experiments are translated to isolated compounds,and the premier cases are the clusters of carbon called the fullerenes, notably clusters with the formula C60, C70,and C84. The fullerene sphere can be filled with smallmolecules, forming Endohedral fullerenes
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29. Reference useful website:( wikipedia website)
Reference books:
1.A.G. Sharpe
2.Cluster Chemistry
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30. Thank you
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