Fullerene chemistry is a field of organic chemistry devoted to the

chemical properties of fullerenes.[1][2][3]. Research in this field is

driven by the need to functionalize fullerenes and tune their
properties. For example fullerene is notoriously insoluble and
adding a suitable group can enhance solubility .[1]. By adding a
polymerizable group, a fullerene polymer can be obtained.
Functionalized fullerenes are divided into two classes: exohedral
with substituents outside the cage and endohedral fullerenes with
trapped molecules inside the cage.

Chemical properties of fullerenes

Fullerene or C60 is soccer-ball-shaped or Ih with 12 pentagons

and 20 hexagons. According to Euler's theorem these 12
pentagons are required for closure of the carbon network
consisting of n hexagons and C60 is the first stable fullerene
because it is the smallest possible to obey this rule. In this
structure none of the pentagons make contact with each other.
Both C60 and its relative C70 obey this so-called isolated
pentagon rule (IPR). The next homologue C84 has 24 IPR
isomers of which several are isolated and another 51,568 non-
IPR isomers. Non-IPR fullerenes have thus far only been
isolated as endohedral fullerenes such as Tb3N@C84 with two
fused pentagons at the apex of an egg-shaped cage [4]
Because of the molecule's spherical shape the carbon atoms are
highly pyramidalized, which has far-reaching consequences for
reactivity. It is estimated that strain energy constitutes 80% of
the heat of formation. The conjugated carbon atoms respond to
deviation from planarity by orbital rehybridization of the sp²
orbitals and pi orbitals to a sp2.27 orbital with a gain in p-
character. The p lobes extend further outside the surface than
they do into the interior of the sphere and this is one of the
reasons a fullerene is electronegative. The other reason is that
the empty low-lying pi* orbitals also have high s character.
The double bonds in fullerene are not all the same. Two groups
can be identified: 30 so-called [6,6] double bonds connect two
hexagons and 60 [5,6] bonds connect a hexagon and a
pentagon. Of the two the [6,6] bonds are shorter with more
double-bond character and therefore a hexagon is often
represented as a cyclohexatriene and a pentagon as a pentalene
or [5]radialene. In other words, although the carbon atoms in
fullerene are all conjugated the superstructure is not a super
aromatic compound. The X-ray diffraction bond length values
are 135.5 pm for the [6,6] bond and 146.7 pm for the [5,6]
bond.
C60 fullerene has 60 pi electrons but a closed shell configuration
requires 72 electrons. The fullerene is able to acquire the
missing electrons by reaction with potassium to form first the
K6C606- salt and then the K12C6012- In this compound the bond
length alternation observed in the parent molecule has
vanished.

Fullerene reactions:

See also: Bingel reaction and Prato reaction

Fullerenes tend to react as electrophiles. An additional driving
force is relief of strain when double bonds become saturated.
Key in this type of reaction is the level of functionalization i.e.
monoaddition or multiple additions and in case of multiple
additions their topological relationships (new substituents
huddled together or evenly spaced).
• Fullerenes react as electrophiles with a host of
nucleophiles in nucleophilic additions. The intermediary
formed carbanion is captured an electrophile. Examples
of nucleophiles are Grignard reagents and organolithium
 reagents. For example the reaction of C60 with
methylmagnesium chloride stops quantitatively at the
penta-adduct with the methyl groups centered around a
cyclopentadienyl anion which is subsequently protonated
[5]
. Another nucleophilic reaction is the Bingel reaction.
• Fullerene reacts with chlorobenzene and aluminium
chloride in a Friedel-Crafts alkylation type reaction. In
this hydroarylation the reaction product is the 1,2-
addition adduct (Ar-CC-H) [6].
• The [6,6] bonds of fullerenes react as dienes or
dienophiles in cycloadditions for instance Diels-Alder
reactions. 4-membered rings can be obtained by
[2+2]cycloadditions for instance with benzyne. An
example of a 1,3-dipolar cycloaddition to a 5-membered
ring is the Prato reaction.
• Fullerenes are easily hydrogenated by several methods
with C60H18 and C60H36 being most studied
hydrofullerenes[citation needed]. However, completely
hydrogenated C60H60 is only hypothetical because of large
strain. Highly hydrogenated fullerenes are not stable,
prolonged hydrogenation of fullerenes by direct reaction
with hydrogen gas at high temperature conditions results
in collapse of cage structure with formation of polycyclic
aromatic hydrocarbons.
• Although more difficult than reduction, oxidation of
fullerene is possible for instance with oxygen and osmium
tetraoxide
• Fullerenes react in electrophilic additions as well. The
reaction with bromine can add up to 24 bromine atoms to
the sphere. The record holder for fluorine addition is
C60F48. According to in silico predictions the as yet
elusive C60F60 may have some of the fluorine atoms in
endo positions (pointing inwards) and may resemble a
tube more than it does a sphere [7]
• Fullerenes react with carbenes to methanofullerenes
Fullerenes as ligands
Fullerene is a ligand in organometallic chemistry . The [6,6] double bond is electron-
deficient and usually forms metallic bonds with η = 2 hapticity. Bonding modes such as η
= 5 or η = 6 can be induced by modification of the coordination sphere.

• C60 fullerene reacts with tungsten hexacarbonyl W(CO)6 to the (η²-C60)W(CO)5

complex in a hexane solution in direct sunlight

[edit] Multistep fullerene synthesis

Although the procedure for the synthesis of the C60 fullerene is well established
(generation of a large current between two nearby graphite electrodes in an inert
atmosphere) a 2002 study described an organic synthesis of the compound starting from
simple organic compounds

In the final step a large polycyclic aromatic hydrocarbon

consisting of 13 hexagons and three pentagons is submitted to
flash vacuum pyrolysis at 1100°C and 0.01 Torr. The three
carbon chlorine bonds serve as free radical incubators and the
ball is stitched up in a no-doubt complex series of radical
reactions. The chemical yield is low: 0.1 to 1%. A small
percentage of fullerenes is formed in any process which
involves burning of hydrocarbons, e.g. in candle burning. The
yield through a combustion method is often above 1%. The
method proposed above does not provide any advantage for
synthesis of fullerenes compared to the usual combustion
method, and therefore, the organic synthesis of fullerenes
remains a challenge for chemistry.
A similar exercise aimed at construction of a C78 cage in 2008
(but leaving out the precursor's halogens) did not result in a
sufficient yield but at least the introduction of Stone Wales
defects could be ruled out [11].

Nanotube chemistry
Carbon nanotubes, also part of the fullerene family, which can
be described as graphene sheets rolled into a cylindrical tube.
Unlike the spherical fullerenes made up of hexagons and
pentagons, nanotubes only have hexagons present but in terms
of reactivity both systems have much in common. Due to
electrostatic forces nanotubes have a nasty tendency to cluster
together into bundles and many potential applications require
an exfoliation process. One way to do this is by chemical
surface modification.
A useful tool for the analysis of derivatised nanotubes is
Raman spectroscopy which shows a G-band (G for graphite)
for the native nanotubes at 1580 cm-1 and a D-band (D for
defect) at 1280 cm-1 when the graphite lattice is disrupted with
conversion of sp² to sp³ hybridized carbon. The ratio of both
peaks ID/IG is taken as a measure of functionalization. Other
tools are UV spectroscopy where pristine nanaotubes show
distinct Van Hove singularities where functionalized tubes do
not and simple TGA analysis.
In one type of chemical modification aniline is oxidized to a
diazonium intermediate which after expulsion of nitrogen
forms a covalent bond as an aryl radical [14] [15]:
Also known are protocols for Diels-Alder reactions, one
assisted by chromium hexacarbonyl and high pressure [16]. The
ID/IG ratio for reaction with Danishefsky’s diene is 2.6.
[edit] Fullerene purification
Fullerene purification is the process of obtaining a fullerene
compound free of contamination. In fullerene production
mixtures of C60, C70 and higher homologues are always formed.
Fullerene purification is key to fullerene science and
determines fullerene prices and the success of practical
applications of fullerenes. The first available purification
method for C60 fullerene was by HPLC from which small
amounts could be generated at large expense.
A practical laboratory-scale method for purification of soot
enriched in C60 and C70 starts with extraction in toluene
followed by filtration with a paper filter. The solvent is
evaporated and the residue (the toluene-soluble soot fraction)
redissolved in toluene and subjected to column
chromatography. C60 elutes first with a purple color and C70
is next displaying a reddish-brown color [17].
In nanotube processing the established purification method for
removing amorphous carbon and metals is by competitive
oxidation (often a sulfuric acid / nitric acid mixture). It is
assumed that this oxidation creates oxygen containing groups
(hydroxyl, carbonyl, carboxyl) on the nanotube surface which
electrostatically stabilize them in water and which can later be
utilized in chemical functionalization. One report [18] reveals
that the oxygen containing groups in actuality combine with
carbon contaminations absorbed to the nanotube wall that can
be removed by a simple base wash. Cleaned nanotubes are
reported to have reduced D/G ratio indicative of less
functionalization, and the absence of oxygen is also apparent
from IR spectroscopy and X-ray photoelectron spectroscopy.