pubs.acs.

org/joc

Synthesis and Regiochemistry of [60]Fullerenyl 2-Methylmalonate

Bisadducts and their Facile Electron-Accepting Properties
Ken Kokubo,*,, Riyah S. Arastoo, Takumi Oshima, Chun-Chih Wang, Yuan Gao,
Hsing-Lin Wang, Hao Geng, and Long Y. Chiang*,

Division of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan,
Physical Chemistry and Spectroscopy Group, Chemistry Division, Los Alamos National Laboratory, Los Alamos,
New Mexico 87545, and Department of Chemistry, University of Massachusetts, Lowell, Massachusetts 01854

kokubo@chem.eng.osaka-u.ac.jp; long_chiang@uml.edu
Received April 30, 2010

A simple one-pot reaction using in situ chemically generated Na-naphthalenide as an electron reductant
in the preferential generation of C602- is described. Trapping of C602- intermediate with 2 molar equiv
of sterically hindered 2-bromo-2-methylmalonate ester afforded two singly bonded fullerenyl bisadducts C60[-CMe(CO2Et)2]2 in 35% and 7% yield, respectively. The regiochemistry of these two
products was determined to be 1,4- and 1,16-bisadducts, respectively, by NMR, UV-vis-NIR,
LCMS, and X-ray single crystal structural analysis. The minor 1,16-bisadduct 2 exhibits long wavelength absorption bands in the near-IR region and prominent electron-accepting characteristics as
compared with those of the major 1,4-bisadduct and pristine C60. As revealed by DFT calculation, we
propose that the origin of these unusual characters of 2 arises from the moiety of [18]-trannulene, in
close resemblance to that of the highly symmetrical emerald green 1,16,29,38,43,60-hexaadduct of C60,
EF-6MCn. Accordingly, we anticipate a fast progressive formation of plausible 1,16-bisadduct-like
intermediate moieties on a C60 cage as the precursor structure leading to the formation of EF-6MCn, by
taking the corresponding regiochemistry and electronic properties into account.

Introduction
Effective methods for fullerene functionalization have been
investigated over the past decade1 aiming at the enhancement
of solubility and compatibility of C60 with the secondary
system. Chemical modification of C60 also broadens the scope

of its participation in electronic and optoelectronic processes

for materials utilities, e.g., photovoltaic cells, organic electroluminescence, and nonlinear optical photonics.2 Thus, the high
interest in determining simple, characterizable methods for the
preparation of novel well-defined fullerene derivatives persists.

(1) (a) Thilgen, C.; Diederich, F. Chem. Rev. 2006, 106, 50495135.
(b) Nakamura, E; Isobe, H. Acc. Chem. Res. 2003, 36, 807815. (c) Hirsch,
A., Ed.; In Fullerenes and Related Structures; Springer: Berlin, 1999; Vol. 199.
(d) Diederich, F.; Thilgen, C. Science 1996, 271, 317323. (e) Hirsch, A.
Synthesis 1995, 895913.

(2) (a) Guldi, D. M.; Illescas, B. M.; Atienza, C. M.; Wielopolski, M.;
Mart n, N. Chem. Soc. Rev. 2009, 38, 15871597. (b) Peet, J.; Heeger, A. J.;
Bazan, G. C. Acc. Chem. Res. 2009, 42, 17001708. (c) Elim, H. I.; Anandakathir, R.; Jakubiak, R.; Chiang, L. Y.; Ji, W.; Tan, L. S. J. Mater. Chem.
2007, 17, 18261838. (d) Mart n, N.; S
anchez, L.; Illescas, B.; Perez, I. Chem.
Rev. 1998, 98, 25272547.

4574

Published on Web 06/04/2010

J. Org. Chem. 2010, 75, 45744583

DOI: 10.1021/jo1007674
r 2010 American Chemical Society

JOC Article

Kokubo et al.
SCHEME 1

Direct reduction of C60 was achieved by transferring one

or multiple electrons from metal or organic donors, leading
to the generation of corresponding C60n- intermediates,3
including C602-, which is a strong electron donor nucleophile
in reaction with electrophiles.4 Such reaction may result in
the product of fullerenyl bisadducts. The mechanism of their
formation was proposed to follow a sequence of stepwise
pathways5 with an initial step reaction involving C602- and
one alkyl halide molecule, giving the monoalkyl adduct
anion, RC60-, via single electron transfer followed by radical
coupling. The second step involved the SN2 reaction of RC60with the second primary or secondary alkyl halide molecule
to afford the corresponding bisadduct derivatives. Chemical
generation of C602- by the thiol donor reduction was plausible
in reported methods using either n-propanethiol-K2CO36 or
sodium alkanethiolate RS-Na (R = Me, n-Pr, n-Bu) as the
reagents.4c-e,7
Recently we reported the reaction of multianionic C60
intermediate (up to C606-)8 with di(tert-butyl) 2-bromo-2methylmalonate to produce a new class of emerald green
fullerenes,9 giving an example of singly bonded hexaadduct
C60[-CMe(CO2-t-Bu)2]6 (EF-6MC4t). Here we report the use
of sodium naphthalenide as an electron reducing agent for
(3) Reed, C. A.; Bolskar, R. D. Chem. Rev. 2000, 100, 10751120.
(4) (a) Subramanian, R.; Kadish, K. M.; Vijayashree, M. N.; Gao, X.;
Jones, M. T.; Miller, M. D.; Krause, K. L.; Suenobu, T.; Fukuzumi, S.
J. Phys. Chem. 1996, 100, 1632716335. (b) Kadish, K. M.; Gao, X.; Van
Caemelbecke, E.; Hirasaka, T.; Suenobu, T.; Fukuzumi, S. J. Phys. Chem. A
1998, 102, 38983906. (c) Allard, E.; Delaunary, J.; Cheng, F.; Cousseau, J.;
Orduna, J.; Garin, J. Org. Lett. 2001, 3, 35033506. (d) Cheng, F.; Murata,
Y.; Komatsu, K. Org. Lett. 2002, 4, 25412544. (e) Allard, E.; Delaunary, J.;
Cousseau, J. Org. Lett. 2003, 5, 22392242. (f) Zheng, M.; Li, F.; Shi, Z.;
Gao, X.; Kadish, K. M. J. Org. Chem. 2007, 72, 25382542.
(5) Fukuzumi, S.; Suenobu, T.; Hirasaka, T.; Arakawa, R.; Kadish,
K. M. J. Am. Chem. Soc. 1998, 120, 92209227.
(6) Subramanian, R.; Boulas, P.; Vijayashree, M. N.; DSouza, F.; Jones,
M. T.; Kadish, K. M. J. Chem. Soc., Chem. Commun. 1994, 18471848.
(7) Allard, E.; Riviere, L.; Delaunary, J.; Dubois, D.; Cousseau, J.
Tetrahedron Lett. 1999, 40, 72237226.
(8) Bhonsle, J. B.; Chi, Y.; Huang, J. P.; Shiea, J.; Chen, B. J.; Chiang,
L. Y. Chem. Lett. 1998, 465466.
(9) (a) Canteenwala, T.; Padmawar, P. A.; Chiang, L. Y. J. Am. Chem.
Soc. 2005, 127, 2627. (b) Canteenwala, T.; Li, W.; Wang, H. L.; Chiang,
L. Y. Chem. Lett. 2006, 35, 762763.

the generation of C602-, followed by its trapping with diethyl

2-bromo-2-methylmalonate to afford novel fullerenyl 1,4bisadduct 1, C60[-CMe(CO2Et)2]2, in a common 1,4-addition
manner along with a minor quantity of 1,16-bisadduct 2 (as a
racemic mixture with its enantiomeric 1,29-bisadduct) in an
unusual 1,6-addition manner,10 as shown in Scheme 1. The
latter minor bisadduct showed a C2-symmetry in the molecular structure consistent with 1,16-substituted fullerenyl sp3
carbon positions that bears a close similarity in regiochemistry, as an adjacent pair of two substituents (1,16 or 1,38), to
a partial structure of 1,16,29,38,43,60-hexaadduct EF6MCn, although the latter Cs-symmetrical 1,38-bisadduct
was absent in the same reaction.
Results and Discussion
Experimentally, the reducing agent was prepared by the
treatment of naphthalene (78 mg, 0.61 mmol) with sodium
metal (>14 mg, 0.61 mmol) in freshly distilled THF (50 mL)
at ambient temperature under N2 or Ar atmosphere. The
solution was stirred until the color changed to dark green.
The resulting Na-naphthalenide solution was transferred
slowly into the deoxygenated solution of C60 (200 mg,
0.28 mmol) in dry toluene (100 mL). The mixture was
allowed to stir for 4.0 h at room temperature, followed by
the addition of diethyl 2-bromo-2-methylmalonate (281 mg,
1.11 mmol). The reaction was continued for an additional
1.0 h. At the end of reaction, the solvent was removed under
reduced pressure, and the residue was purified on a silica gel
column using toluene-THF (98:2) as the eluent to afford a
mixture of C60[-CMe(CO2Et)2]2 1 and 2 as brown solids in a
total yield of 42% and a ratio of ca. 5:1 based on the HPLC
peak area count (5-PBB column, toluene, UV 310 nm). The
unreacted C60 as confirmed by LCMS was recovered in 20%
(10) (a) Kusukawa, T.; Ando, W. Angew. Chem., Int. Ed. Engl. 1996, 35,
13151317. (b) Kusukawa, T.; Ando, W. J. Organomet. Chem. 1998, 561,
109120. (c) Ford, W. T.; Nishioka, T.; Qiu, F.; DSouza, F.; Choi, J.-P.
J. Org. Chem. 2000, 65, 57805184. (d) Maeda, Y.; Rahman, G. M. A.;
Wakahara, T.; Kako, M.; Okamura, M.; Sato, S.; Akasaka, T.; Kobayashi,
K.; Nagase, S. J. Org. Chem. 2003, 68, 67916794. (e) Tajima, Y.; Hara, T.;
Honma, T.; Matsumoto, S.; Takeuchi, K. Org. Lett. 2006, 8, 32033205.

J. Org. Chem. Vol. 75, No. 13, 2010

4575

JOC Article

FIGURE 1.

Kokubo et al.

13

C NMR spectrum of the bisadduct 1.

TABLE 1. Reaction of C60 with Diethyl 2-Bromo-2-Methylmalonate

under Various Conditions
naphthalene anionization malonate reaction conv yield 1/2
time (h)b
(equiv)a
time (h)c (%)d (%)d,e
(equiv)a
2.2
2.2
2.2
2.2
10
10

4
4
2
4
4
4

2
10
10
4
10
10

72
1
4
1
1
12

55
81
76
80
94
100

6
35
40
45
15
0 (25) f

a
Relative to C60 used (0.28 mmol). Sodium was used in excess to naphthalene. bBefore adding malonate. cAfter adding malonate. d Determined
by HPLC based on C60 used. eCombined yield of 1 and 2. f The value in
parentheses is the isolated yield of EF-6MC2 hexaadduct.

yield. Further isolation of 1 and 2 was made by using a

preparative HPLC equipped with a Buckyprep column with
toluene/2-propanol (6:4) as the eluent to afford two products
in a yield of 35% and 7%, respectively.
Reaction conditions were roughly optimized as shown in
Table 1. To generate the dianion of C60 efficiently, 2.2 equiv of
naphthalene relative to C60 was used. When a nearly equal
molar quantity of 2-bromo-2-methylmalonate (2.0 equiv) was
used, both the conversion and the yield of bisadducts 1/2
remained low (55 and 6%, respectively). By employing an
excess amount of malonate (10 equiv), the conversion was
increased up to ca. 80% and the yield was moderately increased
(35-40%). In these conditions, tetraadducts were also obtained
along with bisadducts and unreacted C60 that may provide the
reason why more than 4.0 equiv of malonate is necessary to give
the highest yield (45%) and conversion rate. When an excess
amount of naphthalene (10 equiv) was applied, the conversion
was further increased up to 94% and 100% within the reaction
period of 1.0 and 12 h, respectively. However, due to the
significant increase of multiadducts, the observed yield of 1/2
was reduced to 15% and 0%, respectively. At the end of the
reaction period (12 h) under this condition, the greenish
hexaadduct, EF-6MC2, was isolated in more than 25% yield.
Structural characterization of 1 and 2 was achieved by
various spectroscopic measurements. APPI-LCMS spectra
of bisadducts 1 and 2 both showed a weak peak at m/z 1066,
corresponding to the molecular mass ion of C76H26O8, and
4576

J. Org. Chem. Vol. 75, No. 13, 2010

two clear mass fragmentation peaks at m/z 721 and 893

corresponding to the loss of a CMe(CO2Et)2 and a [CMe(CO2Et)2]2 moiety, respectively, from the molecular mass
ion, however, in different relative peak intensity. In the case
of HRMS (MALDI-TOF), the spectrum showed only fragmentation peaks at m/z 720 and 893 (see Supporting
Information). The 1H NMR spectrum of 1 in CDCl3 basically showed three aliphatic peaks at 4.3 (q) and 1.3 (t) for
the ethyl group and 2.4 (s) for the methyl group, which was
assigned to the diethyl 2-methylmalonate moiety. In more
details, the spectrum also displayed two sets of triplets at
1.31 and 1.34 (6H, J = 7.3 Hz) and two sets of doubletquartets at 4.31 and 4.32 (2H, J = 14.5 and 7.3 Hz) overlapped with one quartet at 4.30 (4H, J = 7.3 Hz). The
pattern implies the presence of two sets of carboethoxy
groups, indicating the different chemical environment between these two sets out of four ethyl groups, consistent with
the plausible CS or C2 symmetry. The complex coupling
pattern of the peak at 4.3 suggested that one of the sets of
carboethoxy groups is suffered from the steric hindrance
caused by the neighboring fullerene moiety, while the other
carboethoxy group is in a rather far position capable of free
rotation. In the case of the minor bisadduct 2, the corresponding peaks in its 1H MMR spectrum were essentially the
same but slightly shifted to the lower field for the ethyl group
and to the higher field for the methyl group, as compared to
those of 1.
More importantly, the 13C NMR spectrum of 1, as shown
in Figure 1, exhibited 30 carbon signals (1 peak of 4C, 25
peaks of 2C, and 4 peaks of 1C) in the range of 138-154 for
the fullerenyl sp2 carbons. Two chemical shifts at 170.2 and
170.1 were assigned to peaks of two sets of carbonyl carbons.
Chemical shift of a tertiary methyl carbon (sp3) of 2-methylmalonate moiety was found to be 20.9 ppm, based on its peak
intensity in a half to that of the terminal ethoxy carbon peak
at 13.9. One carbon peak at 60.4 can be easily assigned to
the quaternary carbon of 2-methylmalonate group due to its
low peak intensity. The number of fullerenyl carbon peaks
revealed a symmetry plane (v) dissecting the molecule with
four sp2 carbons located on the plane. Peaks of these four
carbons, each in a reduced signal intensity, were assigned to the

Kokubo et al.

FIGURE 2.

JOC Article

13

C NMR spectrum of the bisadduct 2.

FIGURE 3. ORTEP drawing of the major 1,4-bisadduct 1.

chemical shift at 140.2, 142.8, 143.0, and 144.3, consistent with

the CS symmetrical structure of 1,4-bisadduct. On the other
hand, the 13C NMR spectrum of 2, as shown in Figure 2,
showed a spectrum similar to that of 1 except for the aromatic
region: the spectrum exhibited 29 carbon signals with almost the
same intensity in the range of 136-160 for the fullerenyl sp2
carbons, indicating a C2 symmetrical structure for this minor
1,16-bisadduct. It is noted that the lowest fielded aromatic peak
located apart at 159.8 was assigned by DFT simulation as 6and 15-position carbons which are adjacent to 2-methylmalonate substituted sp3 carbons at the [5,6]-bond.
Although the calculated 13C NMR patterns in the aromatic region for some bisadduct isomers, based on the DFT
calculation, have predicted the structure of the major bisadduct as CS-symmetrical 1,4- or 1,38-bisadducts,11 influence
of the stereoelectronic effect of substituents as well as the
(11) Kokubo, K.; Thota, S.; Wang, H.-L.; Chiang, L. Y. J. Macromol.
Science, Part A: Pure Appl. Chem. 2009, 46, 11761181.

solvent effect may be ignored to obtain the sufficient prediction. Therefore, we carried out the preparation of a single
crystal for the X-ray crystal structural analysis. When a
mixture of cyclohexane and hexane was used as crystallization cosolvents, we obtained pure single crystals in sufficiently good quality and succeeded in collecting the crystallographic data at 123 K (Figure 3). The crystal included a
molecule of cyclohexane in a lattice of the bisadduct. Subsequent structural analysis confirmed this regioisomer as the
1,4-bisadduct 1, consistent with the 1H and 13C NMR spectroscopic data. The CS symmetrical structure at the fullerene
moiety has a bisected mirror plane as indicated by its 13C
NMR spectrum. However, due to the high steric hindrance at
the sp3 fullerenyl carbon (CF) region with a very limited degree
of freedom for the CF-C(CH3) bond rotation, the configuration of 2-methylmalonate moieties was found to be oriented in
a different C2 symmetry, not the same CS symmetry. This
interesting feature may make the symmetry prediction complicated for fullerenyl bisadducts having a 2-methylmalonate
moiety. Accordingly, two addends of 1 were separated from
each other with the closest H-H and O-O interspacing in a
short distance of 2.580 and 2.831 A, respectively.
Several attempts at the crystallization of the minor bisadduct 2 were conducted without success because of its poor
crystallinity that may be related to its good solubility as
compared with that of 1. Thus, the regiochemistry of the
isomer 2 was determined by the comparison of the
UV-vis-NIR spectrum with those of reported structurally
known bisadducts reported. The UV-vis spectrum of 1 in
THF exhibited four broad absorptions with max at 252, 294,
328, and 445 nm (Figure 4). Since the UV spectrum of the 1,4bisadduct, regardless of the type of addends, typically shows
a broad peak around 443-445 nm, optical absorptions of 1
are consistent with this regioisomeric structure.4e,12
(12) (a) Schick, G.; Kampe, K.-D.; Hirsh, A. J. Chem. Soc., Chem.
Commun. 1995, 20232024. (b) Nagashima, H.; Terasaki, H.; Saito, Y.;
Jinno, K.; Itoh, K. J. Org. Chem. 1995, 60, 49664967. (c) Wang, G.-W.;
Murata, Y.; Komatsu, K.; Wan, T. S. M. Chem. Commun. 1996, 20592060.
(d) Miki, S.; Kitao, M.; Fukunishi, K. Tetrahedron Lett. 1996, 37, 20492052.
(e) Zhang, T.-H.; Lu, P.; Wang, F.; Wang, G.-W. Org. Biomol. Chem. 2003, 1,
44034407.

J. Org. Chem. Vol. 75, No. 13, 2010

4577

JOC Article

FIGURE 4. UV-vis-NIR spectra of the bisadducts 1 (dotted

line), 2 (solid line), and EF-6MC2 (chain line) in THF (0.1 mM).
The spectrum of pristine C60 (bold line) in toluene (0.1 mM) is also
shown for a comparison. The inset is the magnified NIR spectra of
the minor bisadduct 2, EF-6MC2, and C60.

On the other hand, the UV-vis-NIR spectrum of 2 in

THF showed the disappearance of a broad peak at 445 nm
and the extended absorption to longer wavelengths. As
shown in the inset of Figure 4, several absorption bands in
weak intensity were observed at 706, 806, and 900 nm in the
NIR region. Such a characteristic feature is closely similar to
the reported spectrum of the 1,16-bisadduct, where peaks are
reported to be 256, 292, 400, 454, 484, 520, 712, 813, and
912 nm,10c even though the possibility of the 1,38-bisadduct
regioisomer cannot be fully ruled out. Observation of
extended absorption up to more than 900 nm for this 1,16bisadduct 2 is rather rare among many reported [60]fullerene
derivatives (including pristine C60 as shown in Figure 4 as
a comparison), whereas the 1,16,29,38,43,60-hexaadduct
(EF-6MCn) also showed a strong absorption at 850 nm as
shown in Figure 4.9a Since the substituted positions at C(1)
and C(16) are common between the structure of 2 and
EF-6MCn, the all-trans [18]-trannulene moiety existing in
these fullerene derivatives may give the reason for the characteristic similarity in their NIR-absorption characteristics
(Figure 5).13,14
Structural characterization for the minor bisadduct 2 was
also carried out by the comparison of its relative energy
stabilization with other regioisomers via semiempirical computational technique. Accordingly, the heat of formation,
Hf, of plausible 1,2-, 1,4-, 1,16-, and 1,38-bisadducts were
calculated using the MOPAC PM3 method (Figure 6).
Among these four regioisomers, the most stable one was
found to be the 1,4-bisadduct (1947.4 kJ mol-1; the major
product 1) with the second for the 1,16-bisadduct (1976.3 kJ
mol-1; the minor product 2). The energy difference, Hf,
(13) Fokin, A. A.; Jiao, H.; Schleyer, P.; von, R. J. Am. Chem. Soc. 1998,
120, 93649365.
(14) (a) Wei, X.-W.; Avent, A. G.; Boltalina, O. V.; Darwish, A. D.;
Fowler, P. W.; Sandall, J. P. B.; Street, J. M.; Taylor, R. J. Chem. Soc., Perkin
Trans. 2 2002, 4146. (b) Burley, G. A.; Fowler, P. W.; Soncini, A.; Sandall,
J. P. B.; Taylor, R. Chem. Commun. 2003, 30423043. (c) Popov, A.;
Senyavin, V. M.; Troyanov, S. I. J. Phys. Chem. A 2006, 110, 74147421.
(d) Troshin, P. A.; Koeppe, R.; Susarova, D. K.; Polyakova, N. V.;
Peregudov, A. S.; Razumov, V. F.; Sariciftci, N. S. S.; Lyubovskaya, R. N.
J. Mater. Chem. 2009, 19, 77387744. (e) Troshin, P. A.; Khakina, E. A.;
Zhilenkov, A. V.; Peregudov, A. S.; Troshina, O. A.; Kozlovskii, V. I.;
Polyakova, N. V.; Lyubovskaya, R. N. Eur. J. Org. Chem. 2010, 10371045.

4578

J. Org. Chem. Vol. 75, No. 13, 2010

Kokubo et al.

between 1,4- and 1,16-bisadducts is 28.9 kJ mol-1 that is

much smaller than Hf values calculated for the 1,2(128.0) and 1,38-bisadduct (726.5). Therefore, our proposed
structure of 2 as the 1,16-bisadduct is quite reasonable in
addition to the similarity argument of the NIR spectrum,
stated above.
Cyclic voltammetric (CV) profiles of 1, 2, and C60 collected
in o-dichlorobenzene in the presence of tetra-n-butylammonium perchlorate (0.1 M) were shown in Figure 7. The
electrochemical data for three reversible reduction waves of
1 and 2 measured between 0.0 and -2.0 V vs Ag/Ag were
summarized in Table 2. Interestingly, while the first halfwave reduction potential E1red1/2 of 1 (-0.92 V) was shifted
to a negative potential by 0.12 V relative to that of the
pristine C60 (-0.80 V) due to the reduction of -conjugation
from 60 to 58 electrons at the fullerenyl cage moiety, the
E1red1/2 value of 2 (-0.71 V) was found to be shifted to a
positive potential by 0.09 V. Since 2-methylmalonate addends on 1 and 2 are the same alkyl groups, this increased
electron accepting ability of 2 is not originated from the
electron-withdrawing nature of the addend. Such a tendency
was also observed in the second (E2red1/2) and third (E3red1/2)
half-wave reduction potentials.
In connection with the previous report the structurally
similar 1,16-bisadducts may show similar cyclic voltammograms.10c Evidently, the regiochemistry-dependent -conjugation on the C60 cage surface may play an important role in
determining the electron-accepting ability of the regioisomer. Kadish et al. have reported that a difference in the
first reductive potentials (100 mV) between 1,2-(PhCH2)C60
(-0.62 V vs SCE) and 1,4-(PhCH2)C60 (-0.52 V) was considered to be large.4f In our cases, the observed difference in
the potentials between the 1,4-bisadduct 1 and the 1,16bisadduct 2 (210 mV) is much larger than that value, giving
the implication of an unique -conjugation structure of the
latter. Moreover, unsymmetrical electron redox waves were
observed with a current intensity for the E2redp wave at -1.44
and -1.28 V in a doubly higher value than those of the
corresponding E2ox waves in the redox cycle of 1 and 2,
respectively (Figure 7). This observation bore a close resemblance to a similar unsymmetrical CV profile with higher
current intensity for E2redp wave at -1.50 V (vs Fc/Fc)
reported for EF-6MC2.9b The phenomena were interpreted
by the involvement of disproportionation of 12- and (EF6MC2)2- with the neutral 1 and EF-6MC2, respectively, to
produce two molecules of 1- and (EF-6MC2)- during the
reductive cycle. That resulted in an accumulatively higher
number of monoanionic intermediate species available for
the second electron reduction in the reductive cycle. On the
basis of this interpretation, the overall redox wave profiles
agreed well with good reversibility and high stability of 1nwith n e 3.
Higher electron affinity of the 1,16-bisadduct 2 than those
of the 1,4-bisadduct 1 and the pristine C60 revealed by their
cyclic voltammetry was rationalized by the DFT calculation
of the HOMO/LUMO energy at B3LYP/6-31G* level of the
theory (Figure 8). Two model compounds, 1,4-C60H2 and
1,16-C60H2, were used instead of 1 and 2, respectively, in
order to simplify electronic and steric factors of addends as
well as to reduce the calculation time. The order of LUMO
energy level in the sequence of 1,4-C60H2 (-3.13) > C60
(-3.23) > 1,16-C60H2 (-3.31 eV) is highly related to the