M.Sc.

IV Semester
CHO-403
Unit 1:Aromaticity
Part-2
Fullerenes
 Fullerenes
Another class of polynuclear aromatic hydrocarbons is the buckminster-
fullerene (C60). H. W. Kroto and coworkers found that fullerenes C60 and
C70, are highly stable aromatic compounds
Fullerene is the third allotrope of carbon after diamond and graphite. The
allotrope C60 resembles the geodesic dome structure based on hexagons
and pentagons designed by R. Buckminster Fuller thus named as fullerene.

C60 C70

Shape of geodesic dome

structure designed Fuller
Structure and Aromaticity of C60

 Fullerenes are closed hollow cage like molecules with the geometry of a
truncated icosahedron {a polygon with 60 vertices and 32 faces (12 pentagonal +
20 hexagonal)}.
 Each pentagon is separated by hexagons and one carbon atom is present at
each vertex. Each carbon is part of one pentagon and two hexagons.

The name C60 is due to the number of carbon atoms in each polygon:
‫ ٭‬Pentagon rings = 12
Number of carbon atoms = 12 × 5 =60

‫ ٭‬Hexagon rings = 12
Number of carbon atoms = 20 × 6 =120†2=60; (the number is divided by 2
because each carbon atom is shared by two hexagons in C60)

 Each carbon atom of fullerene is sp2 hybridized and forms sigma bonds to
three other carbon atoms i.e. one carbon of pentagon, one carbon of hexagon
and one at the junction of the two polygon. The fourth valence electron lies in a
p-orbital which is perpendicular to the spherical surface.

 The perpendicular p-orbitals with valence electron overlap to form pi-electron

cloud outside and inside the sphere, similar to pi-electron cloud of benzene ring.

 Hence C60 is aromatic and has several aromatic structure.

Electronic structure of C60
Synthesis of fullerenes

 Fullerenes can be synthesized vaporising carbon/graphite rod within

a gas medium (helium atmosphere).

 Mixture of fullerenes particularly C60, C70 are formed which are

separated by solvent extraction.

 Pure C60 can be isolated from this mixture by coloumn

chromatography.
Properties of Fullerenes

• Although each carbon atom is only bonded with three other carbons in a
fullerene molecule , dangling a single carbon atom next to the structure is
not strong enough to break the structure of the fullerene.

• They are quite stable structures and resistant to high temperatures.

•Some reactions for planar aromatic compounds are not observed in

fullerenes for ex. typical aromatic substitution reactions.

• The crystals of C60 are electrically insulating but doping with alkali
metals, they assume various phases of semiconductor, conductor and
superconductor properties.

• The most important feature of alkali metal dopped fullerides is their

superconductivity which is much higher than the other organic
superconductors.
Reactions of Fullerene
 Fullerene Family

•A large number of other fullerenes higher or lower than C60 are also
known hence termed as fullerene family.

•The common clusters are C70, C72, C74, C80, C82, C84 and some other
clusters are also known but are less abundant in experimentally
produced fullerene soot mixture.

•Other common family members are „Bucky babies‟ (C32, C44, C50, C58)
and the „Giant fullerenes‟(C240, C540,C 960 ). The giant size fullerene
structure have been predicted on the basis of computer nucleation
process model.
References

1. T. Roger and D. R. Walton, “The Chemistry of Fullerenes”,

Nature,363, 685(1993).
2. A. Kumar, A. Podhorodecki, J. Misiewicz, D. K. Avasthi, J. C. Pivin,
J. Appl. Physics 105, 024314(2009).
3. Advanced Organic Chemistry by Dr. Jagdamba Singh and L. D. S.
Yadav, Pragati Prakashan, 2010.