Fullerene C60 derivatives as efficient sensitizers of oxidation under the mild conditions of atmospheric air

Article abstract of DOI:10.1134/S1070363217100371

The ability of fullerene C₆₀ and of its derivatives to sensitize oxidation of triphenylphosphine with atmospheric oxygen under sunlight illumination at room temperature was found. Reuse of fullerene conjugates did not lead to reduction in their

Full text of DOI:10.1134/S1070363217100371

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 10, pp. 2497–2499. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © R.N. Malikova, I.M. Sakhautdinov, S.M. Ishbaeva, M.S. Yunusov, 2017, published in Zhurnal Obshchei Khimii, 2017, Vol. 87,
No. 10, pp. 1749–1751.
LETTERS
TO THE EDITOR
Fullerene C60 Derivatives as Efficient
Sensitizers of Oxidation under the Mild Conditions
of Atmospheric Air
R. N. Malikovaa*, I. M. Sakhautdinova, S. M. Ishbaevab, and M. S. Yunusova
a Ufa Institute of Chemistry, Russian Academy of Sciences, pr. Oktyabrya 69, Ufa, 450054 Russia
*e-mail: rolimalika@mail.ru
b Bashkir State University, Ufa, Russia
Received June 15, 2017
Abstract—The ability of fullerene C60 and of its derivatives to sensitize oxidation of triphenylphosphine with
atmospheric oxygen under sunlight illumination at room temperature was found. Reuse of fullerene conjugates
did not lead to reduction in their reactivity; the conjugates were recovered unchanged from the reaction
mixture. The use of a xenon lamp significantly shortened the time of the process.
Keywords: fullerene C60, oxidation, fullerene conjugate, triphenylphosphine, diadamantylidene, xenon lamp
DOI: 10.1134/S1070363217100371
Fullerene C60 and many of its derivatives possess
unusual photophysical properties. Absorption of ultra-
violet and visible light by these compounds leads to a
long-lived excited triplet state, and the energy transfer
from the excited fullerene molecule to the oxygen
molecule causes the formation of a highly reactive
species, singlet oxygen [1–4]. This ability of fullerenes
makes them suitable as efficient sensitizers of singlet
oxygen production [5, 6] rendering possible the
oxidation under mild conditions. The main obstacle to
extensive use of fullerenes is their poor solubility in
many solvents [7–10]. This problem can be addressed
by functionalization of the fullerene core with solu-
bilizing groups [11–15] (Scheme 1).
Scheme 1.
O
O
N
n
O
O
O
4, 5
n = 1 (1, 4), 2 (2, 5), 3 (3).
2497

2498
MALIKOVA et al.
Scheme 2.
Scheme 3.
R-C60, O2
P
P
hν
6
O
1
O
6
+
Herein, we studied the oxidation of triphenyl-
phosphine and diadamantylidene with atmospheric
oxygen in the presence of fullerene conjugates R–C60.
As side substituents served derivatives of maleo-
pimaric acid. The latter is an easily accessible com-
pound which can be synthesized from renewable
feedstock rosin, a wood chemical product, by a Diels–
Alder reaction with maleic acid anhydride [16]. Maleo-
pimaric acid is widely used in technology of paints,
varnishes, and polymer materials [17] and is regarded
as a promising starting compound whose derivatives
are readily soluble in most organic solvents.
7 (62%)
(24%)
(Scheme 2). The oxidation of triphenylphosphine
proceeds under daylight illumination, otherwise the
reaction stops.
Triphenylphosphine oxidation for 32 h in the
presence of fullerene C60 gave triphenylphosphine
oxide in a 91% yield. The calculation took into account
solely the daylight time, since with no exposure to
light only trace amounts of PPh3=O were formed both
at room temperature and under reflux in toluene. In the
presence of moisture in the reaction mixture the
process was inhibited, in which case PPh3=O was
obtained in a 24% yield.
For fullerene conjugates 1–5 synthesized the
solubility in toluene (~0.4 g/mL) proved to be two
orders of magnitude higher than that of fullerene C60
(~0.0026 g/mL). However, to maintain the experi-
mental integrity we used the same amounts of the
reagents and of the solvent (see table).
Our experiments with fullerene conjugates revealed
a stronger sensitizing effect for cyclopentenofullerene
derivatives compared to methanofullerenes. The best
results were obtained for compound 1 with the shortest
carbon bridge between the cyclopentenofullerene and
the maleopimarimide moiety. In this case, already after
5 h PPh3 was completely converted to triphenylphos-
phine oxide (see table).
The reaction was carried out in an open vial made
of medical glass in toluene at room temperature using
a 10-fold excess of PPh3 relative to C60 and R–C60
Oxidation of triphenylphosphine with atmospheric oxygen
in a toluene solution
Yield of
PPh3=O, %
Catalyst
t, °C
hν
Time, h
Xenon lamps are known to produce bright white
light that closely mimics natural daylight [18].
Through the use of a xenon lamp with a 35 W ignition
block the time of the triphenylphosphine oxidation
catalyzed by leader-compound 1 was substantially
reduced to 30 min. Under the same conditions,
diadamantylidene 6 was oxidized to diadamantylidene
epoxide 7 (Scheme 3). The reaction was carried out for
8 h and gave compound 7 in a 62% yield.
–
20
20
+
–
64
64
2
2
С60
С60
С60– Н2О
20
20
+
+
32
32
91
24
С60
С60
110
20
–
–
32
32
5
2
1
1
2
3
4
5
20
20
20
20
20
20
+
5
0.5
13
17
14
16
100
100
100
100
100
100
Xenon lamp
Formation of 7 was proven by NMR spectroscopy,
specifically, by disappearance in the 13C NMR spec-
trum of the 133.17 ppm signal from the carbon of the
multiple bond of 6 and by appearance of the 73.66 ppm
signal characteristic of the carbon atoms of the oxirane
ring.
+
+
+
+
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

FULLERENE C60 DERIVATIVES AS EFFICIENT SENSITIZERS
It was shown in [19] that, during oxidation of
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2-(Tricyclo[3.3.1.1]dec-2-ylidene)tricyclo[3.3.1.1]-
decane 2,2'-epoxide (7). Yield 0.25 g (62%), colorless
crystals, mp 182°C. 13C NMR spectrum, δC, ppm: 27.22
(4CH), 31.71 (4CH), 35.16 (4CH2), 36.83 (2CH2),
37.41 (4CH2), 73.66 (2CH2). Found, %: C 84.39; H
9.90. C20H28O. Calculated, %: C 84.45; H 9.92; O 5.62.
The reaction was run in an FO-1 vial made of NS-3
medical glass. A ClearLight 5000K xenon lamp with a
35 W ignition block was used in the experiments.
The NMR spectra were recorded on a Bruker-AM
500 spectrometer operating at 125.76 MHz (13C), with
tetramethylsilane as internal reference. Elemental
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instrument. The melting point was determined on a
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ACKNOWLEDGMENTS
This study was financially supported by the Russian
Foundation for Basic Research (project no. 14-03-
00180) using the equipment of “Khimiya” Center for
Joint Use of the Ufa Institute of Chemistry, Russian
Academy of Sciences.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017