U.S. patent application number 14/315460 was filed with the patent office on 2015-12-31 for fullerene derivative and method for manufacturing a fullerene derivative.
The applicant listed for this patent is Showa Denko K.K., Tohoku University. Invention is credited to Takeshi IGARASHI, Tienan JIN, Weili SI, Yoshinori YAMAMOTO.
Application Number | 20150376110 14/315460 |
Document ID | / |
Family ID | 54929767 |
Filed Date | 2015-12-31 |
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United States Patent
Application |
20150376110 |
Kind Code |
A1 |
JIN; Tienan ; et
al. |
December 31, 2015 |
FULLERENE DERIVATIVE AND METHOD FOR MANUFACTURING A FULLERENE
DERIVATIVE
Abstract
Disclosed is a fullerene derivative represented by the following
formula (1): ##STR00001## wherein FLN is a fullerene backbone,
R.sup.1 is a substituted or non-substituted alkyl group with a
carbon number less than or equal to 24, and Ar.sup.1 is a
substituted or non-substituted aryl group with a carbon number less
than or equal to 24.
Inventors: |
JIN; Tienan; (Miyagi,
JP) ; SI; Weili; (Miyagi, JP) ; YAMAMOTO;
Yoshinori; (Miyagi, JP) ; IGARASHI; Takeshi;
(Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Showa Denko K.K.
Tohoku University |
Tokyo
Miyagi |
|
JP
JP |
|
|
Family ID: |
54929767 |
Appl. No.: |
14/315460 |
Filed: |
June 26, 2014 |
Current U.S.
Class: |
549/59 ; 549/79;
560/102; 560/56 |
Current CPC
Class: |
C07C 2604/00 20170501;
C07C 69/94 20130101; C07C 67/333 20130101; C07C 67/333 20130101;
C07D 333/24 20130101; C07C 69/94 20130101 |
International
Class: |
C07C 69/78 20060101
C07C069/78; C07D 333/24 20060101 C07D333/24; C07C 69/92 20060101
C07C069/92; C07C 67/333 20060101 C07C067/333 |
Claims
1. A fullerene derivative represented by the following formula (1):
##STR00012## wherein FLN is a fullerene backbone, R.sup.1 is a
substituted or non-substituted aralkyl group with a carbon number
ranging from 2 to 24, and Ar.sup.1 is a substituted or
non-substituted one selected from the group consisting of a phenyl
group, 2-thienyl group, and a bithienyl group with a carbon number
less than or equal to 24, wherein FLN is selected from the group
consisting of C.sub.60, C.sub.70, C.sub.76, C.sub.78, C.sub.82,
C.sub.84, C.sub.90, C.sub.94, C.sub.96, C.sub.120 and C.sub.200,
wherein when the R.sup.1 is the substituted aralkyl group, the
substituent of R.sup.1 is selected from a group consisting of an
aryl group, an alkoxy group, an ester-structure-containing group, a
substituted or non-substituted amino group, an alkenyl group, an
alkynyl group and a halogen atom, and wherein when the Ar.sup.1 is
the substituted one, the substituent of Ar.sup.1 is selected from a
group consisting of an alkyl group, an aryl group, an alkoxy group,
an ester-structure-containing group, a substituted or
non-substituted amino group, an alkenyl group, an alkynyl group and
a halogen atom.
2-3. (canceled)
4. The fullerene derivative as claimed in claim 1, wherein at least
one of R.sup.1 and Ar.sup.1 contains an ester structure.
5. The fullerene derivative as claimed in claim 1, wherein FLN is
C.sub.60.
6. A method for manufacturing a fullerene derivative, comprising: a
step of reacting a fullerene dimer represented by the following
formula (2): ##STR00013## wherein FLN is a fullerene backbone
selected from the group consisting of C.sub.60, C.sub.70..sub.1
C.sub.76, C.sub.78, C.sub.82, C.sub.84, C.sub.90, C.sub.94,
C.sub.96, C.sub.120 and C.sub.200, and R.sup.2 is a substituted or
non-substituted aralkyl group with a carbon number less than or
equal to 24, with an aromatic compound represented by the following
formula (3): H--Ar.sup.2 (3) wherein Ar.sup.2 is a substituted or
non-substituted one selected from the group consisting of a phenyl
group, 2-thienyl group, and a bithienyl group with a carbon number
less than or equal to 24, under presence of an alcohol and a
halogenating agent, wherein when the R.sup.2 is the substituted
aralkyl group, wherein the substituent of R.sup.2 is selected from
a group consisting of an aryl group, an alkoxy group, an
ester-structure-containing group, a substituted or non-substituted
amino group, an alkenyl group, an alkynyl group and a halogen atom,
and wherein when the Ar.sup.2 is the substituted one, wherein the
substituent of Ar.sup.2 is selected from a group consisting of an
alkyl group, an aryl group, an alkoxy group, an
ester-structure-containing group, a substituted or non-substituted
amino group, an alkenyl group, an alkynyl group and a halogen
atom.
7-8. (canceled)
9. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein at least one of R.sup.2 and Ar.sup.2 contains
an ester structure.
10. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein the alcohol is selected from the group
consisting of methanol, ethanol, propanol, isopropanol, and
butanol.
11. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein the halogenating agent is selected from the
group consisting of bromine, N-bromosuccinimide, iodine, and
N-iodosuccinimide.
12. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein the step of reacting is conducted at a
temperature of 0.degree. C. to 100.degree. C.
13. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein the step of reacting is conducted for a time
period of 5 minutes to 200 hours.
14. The fullerene derivative as claimed in claim 1, wherein R.sup.1
is selected from a group consisting of
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and
2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2--.
15. The fullerene derivative as claimed in claim 1, wherein
Ar.sup.1 is selected from a group consisting of anisole,
1,2,3-trimethoxybenzene and thiophene,
3,3'-dihexyl-2,2'-bithiophene.
16. The fullerene derivative as claimed in claim 14, wherein
Ar.sup.1 is selected from a group consisting of anisole,
1,2,3-trimethoxybenzene and thiophene,
3,3'-dihexyl-2,2'-bithiophene.
17. The fullerene derivative as claimed in claim 1, wherein a
combination of R.sup.1 and Ar.sup.1 is, (a)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and anisole, (b)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and
1,2,3-trimethoxybenzene, (c)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and thiophene, (d)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and
3,3'-dihexyl-2,2'-bithiophene, (e)
2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2-- and
anisole, (f)
2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2-- and
1,2,3-trimethoxybenzene, or (g)
2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2-- and
thiophene.
18. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein R.sup.2 is selected from a group consisting of
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and
2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2--.
19. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein Ar.sup.2 is selected from a group consisting of
anisole, 1,2,3-trimethoxybenzene and thiophene,
3,3'-dihexyl-2,2'-bithiophene.
20. The method for manufacturing a fullerene derivative as claimed
in claim 18, wherein Ar.sup.2 is selected from a group consisting
of anisole, 1,2,3-trimethoxybenzene and thiophene,
3,3'-dihexyl-2,2'-bithiophene.
21. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein a combination of R.sup.2 and Ar.sup.2 is, (a)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and anisole, (b)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and
1,2,3-trimethoxybenzene, (c)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and thiophene, (d)
3-CO.sub.2CH.sub.3C.sub.6H.sub.4CH.sub.2-- and
3,3'-dihexyl-2,2'-bithiophene, (e)
2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2-- and
anisole, 2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2--
and 1,2,3-trimethoxybenzene, or (g)
2-CH.sub.3O-4-CO.sub.2CH.sub.3--C.sub.6H.sub.4CH.sub.2-- and
thiophene.
22. The fullerene derivative as claimed in claim 1, wherein when
R.sup.1 is the substituted aralkyl group, the substituent of
R.sup.1 is selected from a group consisting of a phenyl group, a
napthyl group, a methoxy group, an ethoxy group, a butoxy group, a
methoxy carbonyl group, an acetyloxy group, a dimethyl amino group,
a vinyl group and a halogen atom, wherein when Ar.sup.1 is the
substituted one, the substituent of Ar.sup.1 is selected from a
group consisting of a methyl group, an ethyl group, a butyl group,
a phenyl group, a napthyl group, a methoxy group, an ethoxy group,
a butoxy group, a methoxy carbonyl group, an acetyloxy group, a
dimethyl amino group, a vinyl group and a halogen atom.
23. The method for manufacturing a fullerene derivative as claimed
in claim 6, wherein when R.sup.2 is the substituted aralkyl group,
the substituent of R.sup.2 is selected from a group consisting of a
phenyl group, a napthyl group, a methoxy group, an ethoxy group, a
butoxy group, a methoxy carbonyl group, an acetyloxy group, a
dimethyl amino group, a vinyl group and a halogen atom, wherein
when Ar.sup.2 is the substituted one, the substituent of Ar.sup.2
is selected from a group consisting of a methyl group, an ethyl
group, a butyl group, a phenyl group, a napthyl group, a methoxy
group, an ethoxy group, a butoxy group, a methoxy carbonyl group,
an acetyloxy group, a dimethyl amino group, a vinyl group and a
halogen atom.
Description
STATEMENT REGARDING PRIOR DISCLOSURES BY THE INVENTOR OR A JOINT
INVENTOR
[0001] The inventor or a joint inventor made a public disclosure
relating to the invention: a presentation "Regioselective synthesis
of 1,4-bisfunctionalized fullerenes via NBS-promoted oxidation of
fullerene monoradical", 94th Spring Annual Meeting of the Chemical
Society of Japan on Mar. 27, 2014, and a corresponding abstract on
Mar. 12, 2014.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] An aspect of the present invention relates to at least one
of a fullerene derivative and a method for manufacturing a
fullerene derivative.
[0004] 2. Description of the Related Art
[0005] A fullerene discovered in 1985 is a third allotrope of
carbon wherein 60 or more carbon atoms are bonded spherically.
Attention is being paid to a fullerene represented by C.sub.60 or
C.sub.70 as a new functional material for an electronic component,
a drug, a cosmetic, or the like, due to its specific molecular
shape.
[0006] For a method for synthesizing a fullerene, an arc discharge
method, a resistance heating method, a laser evaporation method, a
combustion method, a thermal decomposition method, and the like
have been known, and soot that contains a fullerene is produced in
any of the above manufacturing methods. A fullerene soluble in an
organic solvent, such as C.sub.60, C.sub.70, C.sub.76, C.sub.78,
C.sub.82, or C.sub.84 is obtained by subjecting such soot to
extraction with an organic solvent. Furthermore, it is possible to
modify such a fullerene chemically to improve its solubility in an
organic solvent or water.
[0007] One of promising applications of a fullerene is an organic
photoelectric conversion element, such as an organic thin film
solar cell or an organic photosensor, and in particular, an organic
thin film that is formed in a coating process is actively being
studied and developed because it is expected that its production
cost is low. [6,6]-phenyl-C.sub.61-butyric acid methyl ester (that
may be referred to as "[60]PCBM" below) is a representative
electron acceptor material soluble in an organic solvent and is
frequently used for such applications.
[0008] However, in a case where [60]PCBM is combined with an
electron donor material such as poly(3-hexylthiophene) to fabricate
an organic thin film solar cell, there are problems that it is not
possible to provide a sufficiently high open circuit voltage
(V.sub.oc) because a LUMO level of [60]PCBM is comparatively low
and it is not possible to provide a sufficiently high value of
short circuit current (J.sub.sc) because a molar absorption
coefficient of [60]PCBM in a visible light region is comparatively
small.
[0009] In recent years, attention is being paid to a fullerene
derivative with a substituent introduced at 1,4-positions of a
fullerene backbone (that may be referred to as a "1,4-adduct") as a
fullerene derivative capable of solving such problems. In general,
a 1,4-adduct is such that extension of a 71-electron system on a
fullerene backbone is smaller than that of a 1,2-adduct such as
[60]PCBM and accordingly its LUMO level is comparatively high, so
that it is possible to expect an increase in its open circuit
voltage (Voc). Furthermore, a 1,4-adduct has a characteristic
absorption peak near 450 nm in a visible light region, so that it
is also possible to expect an increase in a short circuit current
(J.sub.sc).
[0010] In general, as an alkyl group is introduced to a fullerene
backbone, its solubility in an organic solvent is improved to
increase its compatibility to a coating process. However, an alkyl
group is consequently disadvantageous for controlling a LUMO level
of a fullerene derivative, because it is difficult to provide a
considerable influence on an electronic state of a fullerene
backbone. On the other hand, as an aryl group is directly
introduced to a fullerene backbone, it is possible to control a
LUMO level of a fullerene derivative comparatively easily because
it is possible for an electronic state of an aryl group to provide
a significant influence on an electronic state of a fullerene
backbone although an effect of improving its solubility in an
organic solvent is small due to its rigidity. Hence, it is possible
to expect that a 1,4-adduct substituted with an alkyl group and an
aryl group at a 1-position and a 4-position of a fullerene backbone
respectively is a fullerene derivative material with a high
solubility and a facilitated control of an electronic state and is
excellent as an acceptor material for a photoelectric conversion
element, but a practical example of synthesizing such a material is
limited.
[0011] In Y. Matsuo et al., Chem. Asian J. 8, 121-128 (2013), a
fullerene derivative substituted with an aryl group and a
silylmethyl group at a 1-position and a 4-position of C.sub.60
respectively is synthesized. A synthesis method in Y. Matsuo et
al., Chem. Asian J. 8, 121-128 (2013) is a method such that C60 is
first reacted with an aryl Grignard reagent, subsequently treated
with water to obtain a hydroarylated body as an intermediate and
further with a strong alkali to eliminate a hydrogen atom therefrom
and thereby produce a fullerene anion, and it is reacted with an
alkyl halide group to obtain a target substance. However, this
method has a problem that the kind of a substituent capable of
being introduced to an alkyl group or an aryl group is limited
because a Grignard reagent, a strong alkali, and the like are used.
In Y. Matsuo et al., Chem. Asian J. 8, 121-128 (2013), only a
fullerene derivative having a substituent could be synthesized
wherein the substituent is an alkoxy group, an alkylamino group, an
alkyl halide group, or a silyl group.
[0012] On the other hand, it becomes clear that a phase separation
structure of a current mainstream bulk-hetero-junction-type
photoelectric conversion element influences a performance of the
element. For a factor influencing a phase separation structure, it
is possible to provide a solubility of a material to be used, a
compatibility among materials, a solvent to be used for coating, a
thermal annealing condition, or the like, and a substituent on a
fullerene derivative is important because a solubility or a
compatibility with a donor material is significantly influenced
thereby. For a representative example of a substituent of a
fullerene derivative for influencing a characteristic of a
photoelectric conversion element, it is possible to provide an
ester structure (an oxycarbonyl group or a carbonyloxy group) for
[60]PCBM. K. Moriwaki at al., Tetrahedron 66, 7316-7321 (2010)
describes that solubilities of fullerene derivatives with no ester
structure, similar to [60]PCBM, in an organic solvent are lower
than that of [60]PCBM and characteristics of photoelectric
conversion elements using these derivatives are different from one
another, and accordingly, suggests that presence or absence of an
ester structure in a fullerene derivative influences a phase
separation structure for a bulk hetero-junction structure. As
described above, a fullerene derivative with an introduced
substituent that contains an ester structure is important for
controlling a phase separation structure for a bulk hetero-junction
structure.
[0013] However, as described above, it is not possible for a
synthesis method described in Y. Matsuo et al., Chem. Asian J. 8,
121-128 (2013) to synthesize a fullerene derivative having a highly
reactive substituent that contains an ester structure. That is, it
has not been possible to realize synthesis of a 1,4-adduct that is
substituted with an alkyl group for ensuring a solubility in an
organic solvent and an aryl group for facilitating a control of a
LUMO level and further contains an ester structure in a portion of
those groups to control a phase separation structure
appropriately.
SUMMARY OF THE INVENTION
[0014] According to one aspect of the present invention, there is
provided a fullerene derivative represented by the following
formula (1):
##STR00002##
wherein FLN is a fullerene backbone, R.sup.1 is a substituted or
non-substituted alkyl group with a carbon number less than or equal
to 24, and Ar.sup.1 is a substituted or non-substituted aryl group
with a carbon number less than or equal to 24.
[0015] According to another aspect of the present invention, there
is provided a method for manufacturing a fullerene derivative,
including a step of reacting a fullerene dimer represented by the
following formula (2):
##STR00003##
wherein FLN is a fullerene backbone and R.sup.2 is a substituted or
non-substituted alkyl group with a carbon number less than or equal
to 24, with an aromatic compound represented by the following
formula (3):
H--Ar.sup.2 (3)
wherein Ar.sup.2 is a substituted or non-substituted aryl group
with a carbon number less than or equal to 24, under presence of an
alcohol and a halogenating agent.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0016] An embodiment of the present invention will be described
below.
[0017] [Fullerene Derivative]
[0018] A fullerene derivative according to an embodiment of the
present invention is represented by the following general formula
(1):
##STR00004##
[0019] In formula (1) described above, FLN represents a fullerene
backbone, R.sup.1 represents a substituted or non-substituted alkyl
group with a carbon number less than or equal to 24, and Ar.sup.1
represents a substituted or non-substituted aryl group with a
carbon number less than or equal to 24. Here, the aryl group may be
a heteroaryl group. Furthermore, it is preferable for at least one
of R.sup.1 and Ar.sup.1 to contain an ester structure (an
oxycarbonyl group or a carbonyloxy group).
[0020] Here, a "fullerene derivative" in an embodiment of the
present invention refers to a compound having a structure in such a
manner that a particular group is added to such a fullerene
backbone thereof, and a "fullerene backbone" refers to a carbon
backbone that composes a closed-shell structure of a fullerene.
[0021] Furthermore, a fullerene derivative according to an
embodiment of the present invention is such that an alkyl group and
an aryl group are directly added to a fullerene backbone thereof to
have a structure represented by general formula (1), and
accordingly, has a characteristic such that a control of a
solubility in each kind of solvent and an electronic state is
facilitated.
[0022] Furthermore, in a case where at least one of R.sup.1 and
Ar.sup.1 has an ester structure, a fullerene derivative according
to an embodiment of the present invention is readily dissolved in a
solvent. Accordingly, it is possible to be used for an application
that uses its solution to form a thin film, for example, an organic
thin film device material, a resist material, or a surface coating
material such as a paint, more preferably than a conventional
fullerene derivative.
[0023] R.sup.1 is a substituted or non-substituted alkyl group and
the number of a carbon atom(s) therein is less than or equal to 24.
In a case where the number of carbon atoms is greater than 24, a
group bonding to a fullerene backbone may be so bulky that it is
difficult to be added to the fullerene backbone. Among them, it is
preferable for the number of carbon atoms to be 2 to 18, and it is
more preferable to be 4 to 18. In a case where the number of carbon
atoms is in the range as described above, it is possible to provide
an advantageous effect of ensuring a solubility and preventing
degradation of a characteristic originating from a fullerene
backbone.
[0024] Furthermore, in a case where an alkyl group has a
substituent, such a substituent is not particularly limited, and it
is possible to provide, for example, an aryl group such as a phenyl
group or a naphthyl group, an alkoxy group such as a methoxy group,
an ethoxy group, or a butoxy group, an ester-structure-containing
group such as a methyloxycarbonyl group or an acetyloxy group, a
substituted or non-substituted amino group such as a dimethylamino
group, an alkenyl group such as a vinyl group, an alkynyl group, or
a halogen atom.
[0025] Among them, a substituent containing an ester structure is
preferable and is excellent in providing a high solubility in an
organic solvent.
[0026] For a specific example of a substituted or non-substituted
alkyl group used as R.sup.1, it is possible to provide a
straight-chain or branched-chain alkyl group such as a methyl
group, an ethyl group, a propyl group, or an isopropyl group, a
cyclic alkyl group such as a cyclopropyl group, a cyclopentyl
group, or a cyclohexyl group, an aralkyl group such as a benzyl
group, or the like.
[0027] Among them, an aralkyl group such as a benzyl group is
preferable, and is excellent in providing a particularly high
solubility in an aromatic solvent that is frequently used in a
process for manufacturing an organic thin film device or the
like.
[0028] Furthermore, a substituted or non-substituted aryl with a
carbon number less than or equal to 24 used as Ar.sup.1 is not
particularly limited, and it is possible to use, for example, a
phenyl group or a heteroaryl group such as a pyridyl group, a
pyrrolyl group, a 2-furyl group, a 2-thienyl group, or a bithienyl
group.
[0029] Among them, a phenyl group, a 2-thienyl group, or a
bithienyl group is preferable, and a phenyl group is more
preferable. In a case where an aryl group is a phenyl group, it is
possible to readily introduce a variety of substituents and be
excellent in providing many options for controlling an electronic
state of a fullerene derivative.
[0030] Furthermore, in a case where an aryl group has a
substituent, such a substituent is not particularly limited and it
is possible to be selected appropriately so that a solubility and
an electronic state of a fullerene derivative is controlled,
wherein it is possible to provide, for example, an alkyl group such
as a methyl group, an ethyl group, or a butyl group, an aryl group
such as a phenyl group or a naphthyl group, an alkoxy group such as
a methoxy group, an ethoxy group, or a butoxy group, an
ester-structure-containing group such as a methyloxycarbonyl group
or an acetyloxy group, a substituted or non-substituted amino group
such as a dimethylamino group, an alkenyl group such as a vinyl
group, an alkynyl group, or a halogen atom.
[0031] For a fullerene derivative according to an embodiment of the
present invention, it is usually possible to use a fullerene
backbone with a carbon number of 60 to 200. For a specific example
thereof, it is possible to provide C.sub.60, C.sub.70, C.sub.76,
C.sub.78, C.sub.82, C.sub.84, C.sub.90, C.sub.94, C.sub.96,
C.sub.120, C.sub.200, or the like. Among them, it is preferable for
a carbon number of a fullerene backbone to be 60 or 70, and
C.sub.60 is more preferable. This is because it is possible for a
smaller carbon number to readily obtain a high purity, and in
particular, it is also possible for C.sub.60 to readily obtain a
higher purity than that of another fullerene backbone.
[0032] [Method for Manufacturing a Fullerene Derivative]
[0033] A method for manufacturing a fullerene derivative according
to an embodiment of the present invention is such that a fullerene
derivative dimer represented by the following formula (2):
##STR00005##
is reacted with an aromatic compound represented by the following
formula (3):
H--Ar.sup.2 (3)
under presence of an alcohol and a halogenating agent to obtain a
fullerene derivative represented by the aforementioned formula
(1).
[0034] In formula (2) described above, FLN represents a fullerene
backbone and R.sup.2 is similar to R.sup.1 described above, wherein
a preferable group for R.sup.2 is also similar to that of
R.sup.1.
[0035] It is possible to obtain a fullerene derivative dimer
represented by formula (2) described above by a publicly known
method (for example, a method described in S. Lu et al., Angew.
Chem. Int. Ed. 51, 802-806 (2012)).
[0036] In formula (3) described above, Ar.sup.2 is similar to
Ar.sup.1 described above, wherein a preferable group for Ar.sup.2
is also similar to that of Ar.sup.1.
[0037] Furthermore, it is preferable for at least one of R.sup.2
and Ar.sup.2 to contain an ester structure.
[0038] For a reaction as described above, it is sufficient to mix a
fullerene derivative dimer represented by formula (2), an aromatic
compound represented by formula (3), an alcohol, and a halogenating
agent in solvent to cause a reaction.
[0039] A reaction temperature is preferably 0 to 100.degree. C.,
more preferably 20 to 100.degree. C., and even more preferably 40
to 100.degree. C. Within this range, it is possible to obtain a
fullerene derivative represented by formula (1) at a high yield
that is excellent in a productivity thereof.
[0040] It is sufficient to conduct a reaction until a time at when
a fullerene derivative represented by formula (1) is produced at a
high yield while proceeding of the reaction is analyzed by means of
a high performance liquid chromatography (HPLC), a thin layer
chromatography (TLC), or the like. A reaction time capable of
normally obtaining a fullerene derivative represented by formula
(1) is preferably 5 minutes to 200 hours, more preferably 10
minutes to 100 hours, and even more preferably 30 minutes to 24
hours.
[0041] An alcohol described above is not particularly limited and
it is possible to use, for example, methanol, ethanol, propanol,
isopropanol, or butanol, wherein methanol is preferable from the
viewpoint of a reaction yield.
[0042] A halogenating agent described above is not particularly
limited and it is possible to provide, for example, a halogen such
as iodine or bromine, an organic halide such as N-bromosuccinimide
or N-iodosuccinimide, or the like, wherein it is preferable to use
N-bromosuccinimide from the viewpoint of an excellent reaction
yield.
[0043] A solvent described above is not particularly limited and it
is possible to use, for example, 1,2-dichlorobenzene or the like.
Furthermore, it is also possible to use, as a solvent, a compound
represented by formula (3), an alcohol and/or a halogenating agent
that is/are used for such a reaction.
PRACTICAL EXAMPLES
[0044] An embodiment of the present invention will specifically be
described below, based on practical examples. Here, an embodiment
of the present invention is not limited to these practical
examples.
Practical Example 1
[0045] --Synthesis of Compound 413
[0046] Anisole (0.54 mL, 5.0 mmol) was added to a mixture of
fullerene derivative dimer 1a (87 mg, 0.05 mmol) obtained by a
method described in S. Lu et al., Angew. Chem. Int. Ed. 51, 802-806
(2012), N-bromosuccinimide (that will be referred to as "NBS",
below) (36 mg, 0.20 mmol), methanol (100 .mu.L), and
1,2-dichlorobenzene (that will be referred to as "ODCB", below) (20
mL) at room temperature under air atmosphere, and subsequently,
stirring was conducted at 70.degree. C. for 6 hours to cause a
reaction. Proceeding of the reaction was traced by means of high
performance liquid chromatography (that will be referred to as
"HPLC" below) and thin layer chromatography. After the reaction, a
reaction mixture was directly purified by means of silica gel
column chromatography (eluent: toluene). After a solvent was
distilled away, an obtained solid was washed with methanol and
dried to obtain compound 4a as a dark brown solid. A yield thereof
was 73%.
[0047] Compound 4a: dark brown solid; dissolvable solvents:
CHCl.sub.3, toluene, ODCB; .sup.1H NMR (400 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 3.92 (3H, s), 3.97 (3H, s), 4.26
(1H, d, J=13.2 Hz), 4.32 (1H, d, J=13.2 Hz), 7.08 (2H, d, J=8.8
Hz), 7.35 (1H, dd, J=7.6 Hz, 7.6 Hz), 7.68 (1H, d, J=7.6 Hz), 7.84
(1H, d, J=7.6 Hz), 8.05 (1H, d, J=7.6 Hz), 8.11 (1H, s); .sup.13C
NMR (100 MHz, CDCl.sub.3/CS.sub.2=1/4) .delta. 47.79, 51.41, 54.74,
59.59, 114.62, 127.52, 127.89, 128.40, 129.9, 131.08, 132.48,
134.33, 135.43, 138.06, 141.91, 142.04, 142.17, 142.64, 142.77,
142.81, 143.57, 143.62, 143.64, 143.71, 143.91, 144.41, 146.49,
146.55, 146.59, 148.19, 148.26, 150.92, 158.98; HRMS (ESI,
positive) C76H16O3Na [M+Na]+: 999.0992, found 999.0992.
[0048] A reaction of compound 3a with an anisole as a nucleophile
under presence of NBS was further studied (see Table 1 and formula
(4) described below).
Practical Example 2
[0049] Anisole (0.54 mL, 5.0 mmol) was added to a mixture of
fullerene derivative dimer 1a (87 mg, 0.05 mmol) obtained by a
method described in S. Lu et al., Angew. Chem. Int. Ed. 51, 802-806
(2012), NBS (20 mg, 0.11 mmol), methanol (100 .mu.L), and ODCB (20
mL) at room temperature under air atmosphere, and subsequently,
stirring was conducted at 50.degree. C. for 20 hours to cause a
reaction. A yield of each component after the reaction was
calculated by means of HPLC using C.sub.60 as an internal standard.
The results are illustrated in Table 1. Compound 4a was a main
product and was obtained at a yield of 55%. In addition,
alkoxy-group-containing compound 3a (yield: 2%) and
hydroxyl-group-containing compound 2a (yield: 3%) were
obtained.
[0050] Compound 3a: dark brown solid; dissolvable solvents:
CHCl.sub.3, toluene, ODCB; .sup.1H NMR (400 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 3.94 (3H, s), 4.07 (3H, s), 4.37
(1H, d, J=12.8 Hz), 4.43 (1H, d, J=12.8 Hz), 7.54 (1H, dd, J=7.6
Hz, 7.6 Hz), 7.80 (1H, d, J=7.6 Hz), 8.05 (1H, d, J=7.6 Hz), 8.22
(1H, s); .sup.13C NMR (100 MHz, CDCl.sub.3/CS.sub.2=1/4) .delta.
48.43, 51.61, 54.03, 59.31, 80.72, 127.20, 128.11, 128.46, 130.08,
130.13, 131.4, 134.76, 135.43, 138.24, 139.37, 139.56, 140.40,
141.07, 141.68, 141.84, 142.15, 142.17, 142.2, 142.48, 142.51,
142.53, 142.63, 142.8, 142.84, 142.86, 142.91, 143.00, 143.34,
143.55, 143.60, 143.63, 143.80, 143.81, 143.85, 144.05, 144.12,
144.49, 144.63, 145.14, 145.31, 145.95, 146.16, 146.29, 146.44,
146.54, 146.58, 146.71, 146.80, 146.87, 147.22, 148.01, 148.49,
149.03, 153.01, 153.98, 165.65; HRMS (ESI, positive) C70H12O3
[M+Na]+: 923.0679, found 923.0672.
Comparative Example 1
[0051] Reaction was caused similarly to Practical Example 2 except
that N,N-dimethylformamide (that will be referred to as "DMF",
below) was used instead of methanol. The results are illustrated in
Table 1. Compound 4a could not be obtained and compound 2a was
obtained at a yield of 41% as a main product.
TABLE-US-00001 TABLE 1 Reaction 4a 3a 2a 1a Co- time Yield yield
Yield yield solvent (h) (%) (%) (%) (%) Practical MeOH 20 55 2 3 12
Example 2 Comparative DMF 20 Trace 0 41 18 Example 1
##STR00006##
[0052] Then, the cases where various kinds of nucleophiles were
used instead of anisole in this reaction were studied (see Table 2
and formula (5)).
Practical Examples 3-8
[0053] Reaction was caused similarly to Practical Example 1 except
that compound la or compound 1e (that was each obtained by a method
described in S. Lu et al., Angew. Chem. Int. Ed. 51, 802-806
(2012)) was used as a raw material fullerene derivative dimer and
compounds illustrated in Table 2 were used as nucleophiles instead
of anisole. The results are also illustrated in Table 2. Compounds
4b-4g described below were obtained at good yields.
[0054] Compound 4b: dark brown solid; .sup.1H NMR (400 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 3.93 (3H, s), 3.97 (3H, s), 4.01
(3H, s), 4.14 (3H, s), 4.22 (1H, d, J=12.8 Hz), 4.27 (1H, d, J=12.8
Hz), 6.76 (1H, d, J=8.8 Hz), 7.36 (1H, dd, J=7.6, 7.6 Hz), 7.60
(1H, d, J=8.8 Hz), 7.69 (1H, d, J=7.2 Hz), 7.84 (1H, d, J=7.6 Hz),
8.2 (1H, s); .sup.13C NMR (100 MHz, CDCl.sub.3/CS.sub.2=1/4)
.delta. 47.44, 51.47, 55.36, 59.38, 60.01, 60.27, 106.9, 122.83,
127.79, 128.28, 129.9, 131.22, 134.36, 135.69, 137.9, 138.03,
138.11, 138.24, 140.32, 141.35, 141.63, 141.73, 142.09, 142.25,
142.29, 142.45, 142.63, 142.69, 142.72, 142.73, 142.84, 143.28,
143.38, 143.41, 143.55, 143.61, 143.66, 143.85, 143.87, 143.91,
144.04, 144.13, 144.16, 144.26, 144.49, 144.65, 144.77, 145.02,
145.05, 145.5, 146.36, 146.44, 146.49, 146.52, 146.57, 146.7,
146.77, 146.8, 148.07, 148.11, 148.15, 149.97, 152.7, 153.7,
155.63, 156.03, 165.31; HRMS (ESI, positive) C78H20O5Na [M+Na]+:
1059.1203, found 1059.1200.
[0055] Compound 4c: dark brown solid: dissolvable solvents:
CHCl.sub.3, toluene, ODCB; .sup.1H NMR (400 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 3.92 (3H, s), 4.38 (1H, d, J=12.8
Hz), 4.51 (1H, d, J=12.8 Hz), 7.25-7.27 (1H, m), 7.43 (1H, dd,
J=7.6, 8.0 Hz), 7.52-7.53 (1H, m), 7.68-7.69 (1H, m), 7.79 (1H, d,
J=7.6 Hz), 7.95 (1H, d, J=7.6 Hz), 8.20 (1H, s); .sup.13C NMR (100
MHz, CDCl.sub.3/CS.sub.2=1/4) 6 48.00, 51.40, 56.85, 59.48, 125.39,
125.42, 127.49, 127.92, 128.44, 129.98, 131.20, 134.43, 135.37,
136.64, 137.92, 138.17, 138.71, 140.59, 141.53, 141.66, 141.82,
141.94, 142.07, 142.11, 142.23, 142.26, 142.69, 142.71, 142.73,
142.8, 143.29, 143.38, 143.44, 143.58, 143.71, 143.75, 143.81,
143.83, 143.89, 143.96, 143.98, 143.99, 144.03, 144.22, 144.37,
144.69, 144.79, 145.12, 145.15, 145.51, 145.92, 146.45, 146.55,
146.66, 146.68, 146.76, 147.51, 147.95, 148.2, 148.25, 150.05,
150.45, 155.12, 155.47, 165.08; HRMS (ESI, positive) C73H12O2SNa
[M+Na]+: 975.0450, found 975.0450.
[0056] Compound 4d: .sup.13C NMR (100 MHz, CDCl.sub.3/CS.sub.2=1/4)
.delta. 8.19, 14.33, 22.97, 22.98, 29.06, 29.31, 29.42, 29.53,
30.88, 30.92, 31.82, 31.88, 48.08, 51.4, 59.42, 125.64, 127.12,
127.71, 127.97, 128.36, 129.05, 129.97, 131.27, 134.43, 135.43,
136.92, 137.98, 138.32, 138.71, 140.61, 141.67, 141.82, 141.98,
142.05, 142.13, 142.26, 142.59, 142.69, 142.74, 142.91, 143.29,
143.43, 143.47, 143.62, 143.68, 143.82, 143.85, 143.91, 144,
144.06, 144.42, 144.71, 144.87, 145.15, 145.58, 146.15, 146.5,
146.58, 146.73, 148.28, 150.4, 155, 155.12, 165.15.
[0057] Compound 4e: dark brown solid; dissolvable solvents:
CHCl.sub.3, toluene, ODCB; .sup.1H NMR (400 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 3.84 (3H, s), 3.94 (3H, s), 3.95
(3H, s), 4.35 (1H, d, J=12.4 Hz), 4.39 (1H, d, J=12.4 Hz), 7.10
(2H, d, J=8.4 Hz), 7.45-7.49 (2H, m), 7.55 (1H, d, J=7.6 Hz), 8.12
(2H, d, J=8.8 Hz); .sup.13C NMR (100 MHz, CDCl.sub.3/CS.sub.2=1/4)
.delta. 42.06, 51.91, 55.10, 55.18, 59.55, 60.93, 111.61, 114.66,
121.95, 127.81, 129.43, 130.51, 131.93, 133.27, 136.39, 137.56,
140.59, 142.11, 142.32, 142.43, 142.50, 142.86, 142.96, 143.56,
143.69, 143.77, 143.86, 143.90, 143.99, 144.09, 144.17, 144.21,
144.42, 144.75, 144.80, 145.27, 145.36, 145.97, 146.32, 146.32,
146.65, 146.68, 146.76, 146.82, 146.86, 148.18, 148.42, 148.61,
150.92, 157.49, 159.15, 165.08; HRMS (ESI, positive) C77H18O4Na
[M+Na].sup.+: 1029.1097, found 1029.1098.
[0058] Compound 4f: dark brown solid; .sup.1H NMR (400 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 3.88 (3H, s), 3.91 (3H, s), 3.97
(3H, s), 4.10 (3H, s), 4.29 (1H, d, J=12.4 Hz), 4.33 (1H, d, J=12.0
Hz), 6.70 (1H, d, J=8.4 Hz), 7.43-7.45 (2H, m), 7.51 (1H, d, J=7.6
Hz), 7.58 (1H, dd, J=6.4, 8.0 Hz); .sup.13C NMR (100 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 41.49, 51.3, 54.77, 55.25, 59.1,
59.74, 60.04, 106.76, 111.42, 121.79, 122.83, 127.36, 129.18,
130.19, 131.57, 137.16, 137.64, 141.67, 141.75, 142.11, 142.16,
142.21, 142.24, 142.35, 142.57, 142.59, 142.69, 142.77, 143.33,
143.35, 143.37, 143.59, 143.69, 143.48, 143.89, 143.92, 143.94,
144.11, 144.24, 144.54, 144.56, 144.95, 144.97, 146.27, 146.39,
146.51, 146.53, 146.64, 146.69, 147.55, 148.01, 148.11, 148.22,
150.77, 152.56, 153.51, 156.25, 156.75, 157.09, 164.97; HRMS (ESI,
positive) C79H22O6Na [M+Na]+: 1089.1309, found 1089.1309.
[0059] Compound 4g: dark brown solid; .sup.1H NMR (400 MHz,
CDCl.sub.3/CS.sub.2=1/4) .delta. 3.87 (3H, s), 3.94 (3H, s), 4.48
(1H, d, J=12.4 Hz), 4.55 (1H, d, J=12.8 Hz), 7.25-7.29 (1H, m),
7.52-7.55 (3H, m), 7.62 (1H, d, J=7.6 Hz), 7.73 (1H, s); .sup.13C
NMR (100 MHz, CDCl.sub.3/CS.sub.2=1/4) .delta. 42.05, 51.39, 54.67,
59.19, 111.42, 121.75, 125.27, 125.33, 127.31, 128.88, 130.59,
131.79, 136.66, 137.26, 137.83, 140.52, 141.54, 141.83, 142,
142.11, 142.16, 142.25, 142.72, 142.74, 142.77, 143.28, 143.38,
143.47, 143.49, 143.62, 143.76, 143.82, 143.85, 143.88, 143.94,
144.09, 144.16, 144.4, 144.51, 144.79, 145.04, 145.14, 146.01,
146.23, 146.43, 146.47, 146.49, 146.58, 146.65, 146.73, 147.57,
147.89, 149.14, 150.57, 156.26, 157.18, 165.09; HRMS (ESI,
positive) C74H14O3SNa [M+Na]+: 1005.0556, found 1005.0556.
##STR00007##
[0060] Chemical formulas of compounds 4b-4g are illustrated
below.
##STR00008## ##STR00009##
TABLE-US-00002 TABLE 2 Reaction Product/ time Yield Dimer
Nucleophile (h) (%) Practical 1a 1,2,3- 12 4b/83 Example 3
trimethoxybenzene Practical 1a Thiophene 14 4c/84 Example 4
Practical 1a 3,3'-dihexyl-2,2'- 24 4d/47 Example 5 bithiophene
Practical 1e Anisole 10 4e/40 Example 6 Practical 1e 1,2,3- 24
4f/70 Example 7 trimethoxybenzene Practical 1e Thiophene 18 4g/56
Example 8
Practical Example 9
[0061] Reduction potentials of fullerene derivatives in the
aforementioned practical examples were measured by means of cyclic
voltammetry (that will be referred to as "CV" below). Values of
electric potential with reference to a value of an Fc/Fc+ redox
couple are illustrated in Table 3.
[0062] <CV Measurement Conditions>
[0063] Auxiliary electrolyte: 0.1M Bu.sub.4N.sup.+PF.sub.6.sup.- in
ODCB
[0064] Temperature: 25 degrees
[0065] Scanning speed: 0.02 V/s
[0066] Electrodes: glassy carbon (working electrode), platinum wire
(counter electrode), Ag/Ag.sup.- electrode (reference
electrode)
[0067] Energy levels of lowest unoccupied molecular orbitals (that
will be referred to as "LUMO", below) of 1,4-adducts that were
fullerene derivatives in the aforementioned practical examples were
estimated from first reduction potentials (E.sup.1.sub.1/2)
measured by means of CV. The energy levels of LUMO were calculated
by using the following formula:
Energy level of LUNO=-(E.sup.1.sub.1/2+4.8-E.sup.FC/Fc +)eV.
The results are illustrated in Table 3.
[0068] Each of 1,4-adducts in the aforementioned practical examples
exhibited three quasi-reversible reduction waves similarly to
[6,6]-phenyl-C.sub.61-butyric acid methyl ester (that will be
referred to as [60]PCBM, below). Compound 4b and Compound 4f that
had an electron-donating group on a phenyl group exhibited energy
levels of LUMO comparable to that of [60]PCBM (-3.59 eV). The other
1,4-adducts that had a bithiophene ring or a thiophene ring
exhibited comparatively lower energy levels of LUMO. These results
suggested that an electrochemical characteristic of a 1,4-adduct
according to an embodiment of the present invention could be
adjusted by adding various functional groups thereto.
TABLE-US-00003 TABLE 3 Compound E.sup.1.sub.1/2 (V) E.sup.2.sub.1/2
(V) E.sup.3.sub.1/2 (V) LUMO (eV) 4a -0.52 -0.97 -1.47 -3.64 4b
-0.57 -1.00 -1.55 -3.59 4c -0.49 -0.96 -1.46 -3.67 4d -0.50 -0.93
-1.39 -3.66 4f -0.57 -1.00 -1.52 -3.59 4g -0.50 -0.95 -1.46
-3.66
[0069] [Appendix]
[0070] <A Fullerene Derivative and a Method for Manufacturing a
Fullerene Derivative>
[0071] An illustrative embodiment of the present invention may
relate to at least one of a fullerene derivative and a method for
manufacturing a fullerene derivative.
[0072] One object of an illustrative embodiment of the present
invention may be to provide a fullerene derivative with an alkyl
group and an aryl group that are directly added to a fullerene
backbone thereof, and a manufacturing method thereof.
[0073] Another object of an illustrative embodiment of the present
invention may be to provide a fullerene derivative with an alkyl
group and an aryl group that are directly added to a fullerene
backbone thereof, wherein it is possible to synthesize the
fullerene derivative on a mild condition rapidly, and a
manufacturing method thereof. Additionally, an alkyl group or an
aryl group that is directly added to a fullerene backbone thereof,
as described above, may have a substituent unless otherwise
noted.
[0074] An illustrative embodiment of the present invention may be
at least one of Illustrative Embodiments (1) to (13) described
below.
[0075] Illustrative Embodiment (1) is a fullerene derivative
represented by the following formula (1):
##STR00010##
(In formula (1), FLN represents a fullerene backbone, R.sup.1
represents a substituted or non-substituted alkyl group with a
carbon number less than or equal to 24, and Ar.sup.1 represents a
substituted or non-substituted aryl group with a carbon number less
than or equal to 24. Herein, the aryl group may be a heteroaryl
group.).
[0076] Illustrative Embodiment (2) is the fullerene derivative as
described in Illustrative Embodiment (1), wherein R.sup.1 is a
substituted or non-substituted aralkyl group with a carbon number
less than or equal to 24.
[0077] Illustrative Embodiment (3) is the fullerene derivative as
described in Illustrative Embodiment (1), wherein Ar.sup.1 is
selected from the group consisting of a phenyl group, 2-thienyl
group, and a bithienyl group.
[0078] Illustrative Embodiment (4) is the fullerene derivative as
described in Illustrative Embodiment (1), wherein at least one of
R.sup.1 and Ar.sup.1 contains an ester structure.
[0079] Illustrative Embodiment (5) is the fullerene derivative as
described in Illustrative Embodiment (1), wherein FLN is
C.sub.60.
[0080] Illustrative Embodiment (6) is a method for manufacturing a
fullerene derivative, which includes a step of reacting a fullerene
dimer represented by the following formula (2):
##STR00011##
(In formula (2), FLN represents a fullerene backbone and R.sup.2
represents a substituted or non-substituted alkyl group with a
carbon number less than or equal to 24.) with an aromatic compound
represented by the following formula (3):
H--Ar.sup.2 (3)
(In formula (3), Ar.sup.2 represents a substituted or
non-substituted aryl group with a carbon number less than or equal
to 24. Herein, the aryl group may be a heteroaryl group.) under
presence of an alcohol and a halogenating agent.
[0081] Illustrative Embodiment (7) is the method for manufacturing
a fullerene derivative as described in Illustrative Embodiment (6),
wherein R.sup.2 is a substituted or non-substituted aralkyl group
with a carbon number less than or equal to 24.
[0082] Illustrative Embodiment (8) is the method for manufacturing
a fullerene derivative as described in Illustrative Embodiment (6),
wherein Ar.sup.2 is selected from the group consisting of a phenyl
group, 2-thienyl group, and a bithienyl group.
[0083] Illustrative Embodiment (9) is the method for manufacturing
a fullerene derivative as described in Illustrative Embodiment (6),
wherein at least one of R.sup.2 and Ar.sup.2 contains an ester
structure.
[0084] Illustrative Embodiment (10) is the method for manufacturing
a fullerene derivative as described in Illustrative Embodiment (6),
wherein the alcohol is selected from the group consisting of
methanol, ethanol, propanol, isopropanol, and butanol.
[0085] Illustrative Embodiment (11) is the method for Manufacturing
a fullerene derivative as described in Illustrative Embodiment (6),
wherein the halogenating agent is selected from the group
consisting of bromine, N-bromosuccinimide, iodine, and
N-iodosuccinimide.
[0086] Illustrative Embodiment (12) is the method for manufacturing
a fullerene derivative as described in Illustrative Embodiment (6),
wherein the step of reacting is conducted at a temperature of
0.degree. C. to 100.degree. C.
[0087] Illustrative Embodiment (13) is the method for manufacturing
a fullerene derivative as described in Illustrative Embodiment (6),
wherein the step of reacting is conducted for a time period of 5
minutes to 200 hours.
[0088] According to one illustrative embodiment of the present
invention, it may be possible to provide a fullerene derivative
with an alkyl group and an aryl group that are directly added to a
fullerene backbone thereof, which is capable of being simply and
inexpensively obtained on a mild condition by reacting an alkylated
fullerene dimer with an alcohol, a specific halogenating agent, and
an aromatic compound.
[0089] According to another illustrative embodiment of the present
invention, it may be possible to provide a method for manufacturing
a fullerene derivative wherein a fullerene derivative having a
substituent that further contains an ester structure or the like
therein is also synthesized readily.
[0090] According to another illustrative embodiment of the present
invention, it may be possible to provide a photoelectric conversion
element with an efficiency improved by using a fullerene derivative
according to an illustrative embodiment of the present invention,
because a fullerene derivative represented by the formula (1)
described above is such that a control of a solubility in each kind
of solvent and an electronic state is facilitated by introducing an
alkyl group and an aryl group thereto and further it is also
possible for such a substituent to contain an ester structure or
the like so that a phase separation structure for a bulk
hetero-junction structure is controlled.
[0091] According to another illustrative embodiment of the present
invention, it may be possible to provide a fullerene derivative
that is preferably used for a variety of applications such as an
electronic material, a semiconductor body, a bioactive material, or
the like.
[0092] Although the illustrative embodiment(s) and specific
example(s) of the present invention have been described with
reference to the accompanying drawing(s), the present invention is
not limited to any of the illustrative embodiment(s) and specific
example(s), and the illustrative embodiment(s) and specific
example(s) may be altered, modified, or combined without changing
the essence of or departing from the scope of the present
invention.
* * * * *