Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 1, pp. 159−160.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.G. Atovmyan, A.A. Grishchuk, T.N. Fedotova, Yu.N. Chirkova, Ya.I. Estrin, 2012, published in Zhurnal Prikladnoi Khimii, 2012,
Vol. 85, No. 1, pp. 166−167.
Synthesis of (Polycyanoisopropyl)fullerene
E. G. Atovmyan, A. A. Grishchuk, T. N. Fedotova,
Yu. N. Chirkova, and Ya. I. Estrin
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received May 13, 2011
Abstract—The reaction of fullerene with excess 2,2'-azobis(isobutyronitrile) in o-dichlorobenzene at 60°С was
studied, and the chemical structure of the reaction product was determined.
Spherical fullerene molecule consisting of 60
-hybridized carbon atoms readily enters into various
types of addition reactions, including radical reactions.
A typical source of radicals in liquid-phase reactions
is 2,2'-azobis(isobutyronitrile) (AIBN). Its thermal
degradation results in the release of a nitrogen molecule
and generation of two cyanoisopropyl (CIP) radicals.
A part of the radicals undergoes addition to a fullerene
molecule, and the other radicals recombine to form two
products: tetramethylsuccinodinitrile (TMSDN) and
ketenimine . The ﬁ rst product readily sublimes and
is deposited on a cooled surface in the form of colorless
needle-like crystals. The second product is nonvolatile
but unstable. Its traces can be detected by the IR band
at 2018 cm
According to published data [2, 3], the addition of
CIP radicals to С
at a relatively low molar ratio С
AIBN = 1 : 5 yielded three isomers of the composition
, in which CIP groups were located in
positions 1,2, 1,4, and 1,16. These isomers can transform
into the corresponding polymers .
Interest in nitrile derivatives of fullerene is caused by
the possibility of their subsequent use for the synthesis
of star-shaped fullerene-containing polymers by grafting
linear oligomers to the modiﬁ ed nitrile groups.
The goal of this study was the synthesis of
cyanoisopropylfullerene (CIPF) with more than two
substituents added, without formation of polymers.
For the CIPF synthesis, we used 99.8% pure С
Limited Liability Company, Nizhni Novgorod, Russia).
It was dissolved in o-dichlorobenzene (DCB) puriﬁ ed
by the standard procedure, to obtain a 17 mg ml
(0.023 M) solution. The amount of AIBN (recrystallized
from methanol) introduced into the solution was chosen
so as to obtain its molar concentration exceeding that
by a factor of 7–30. The reaction was performed
in sealed evacuated ampules at 60°С for 5 days, i.e., up
to practically complete decomposition of AIBN. The
dark brown solution formed was heat-treated in a deep
vacuum to remove the solvent and recombination
products of CIP radicals. The black CIPF powder
remaining in the ampule is soluble in the majority of
organic solvents. Its chemical structure was determined
by UV, IR, and
С NMR spectroscopy, size-exclusion
chromatography, and elemental analysis.
The shape of the UV spectrum (Specord M-40
spectrophotometer, solvent toluene) in the range 290–
700 nm (smooth descending curve) indicates that the
samples contained no unchanged fullerene.
The IR spectra of CIPF samples pelletized with KBr
(Bruker Alfa Fourier spectrometer) were compared
with the spectra of AIBN and recombination products
of CIP radicals (mainly TMSDN) in the range 3000–
. All the spectra are sets of band groups
characteristic of CIP fragment (С–Н stretching and