JP2007137809A - Fullerene derivative, method for producing fullerene derivative, nano-mesoscopic material and method for producing nano-mesoscopic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fullerene derivative favorable for design of a new nano-mesoscopic material and to provide a method for producing the derivative. <P>SOLUTION: The fullerene derivative comprises a pyrrolidine ring which contains a binding site (R) for binding a fullerene site (A) to an alkyl chain site (B) and is condensed with a benzene ring. The fullerene derivative is represented by formula (1) [wherein, X is a hydrogen atom or a methyl group; the binding site (R) has at least the one benzene ring; the alkyl chain site (B) is maintained substantially on a plane; and each of at least one alkyl substituent of the alkyl chain site (B) extends in the substantially same direction]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fullerene derivative, a nano mesoscopic material using the fullerene derivative, and a production method thereof. More specifically, the present invention relates to a fullerene derivative having sites having different collective forces, a nano mesoscopic material having various dimensions using the derivative, and a method for producing them.

  Nanocarbons represented by fullerenes, carbon nanotubes, and carbon nanohorns are expected to be applied to electronic materials, electrode materials, catalysts, and biomaterials, and are attracting attention.

Fullerene derivatives with various substituents added to fullerene have been synthesized, and further functions have been revealed. For example, there is a fullerene derivative in which 6 or 7 organic groups having 1 to 20 carbon atoms are bonded (see, for example, Patent Document 1). The fullerene derivative described in Patent Document 1 is obtained by reacting fullerene C ₆₀ or C ₇₀ with a monovalent organic copper reagent. Such fullerene derivatives are useful for electronic materials, physiologically active substances, structural units for forming nanostructures, and the like.

  Moreover, it can be applied to catalytic activity by complexing fullerene derivatives with metal ions.

There is also an example in which a thin line is formed using another fullerene derivative (see, for example, Patent Document 2). The fullerene derivative described in Patent Document 2 can be, for example, a C ₆₀ malonic acid diethyl ester derivative, a C ₆₀ N-methylpyrrolidine derivative, a C ₆₀ ferrocene derivative, or a C ₆₀ platinum derivative. As for the fine lines based on these fullerene derivatives, fullerene derivative fine lines having high crystallinity and a long fiber length can be obtained by a liquid-liquid interface method using a fullerene derivative solution or a mixed solution of fullerene derivatives and fullerenes. The electrical and chemical properties of such fine wires can be controlled by changing the functional group of the fullerene derivative. Further, such a fine wire has high crystallinity and thus acts as a high-quality semiconductor.
JP 2005-232165 A Japanese Patent Laying-Open No. 2005-12776

  The fullerenes and fullerene derivatives described above are expected to be used in nano-mesoscopic electronic components. However, although the technique described in Patent Document 1 suggests a fullerene derivative as a structural unit for nanostructure formation, it has not led to the development of a specific nanostructure formation technique. On the other hand, although the technique described in Patent Document 2 can produce a thin line that is a one-dimensional structure using a fullerene derivative, it cannot form a structure of another dimension. Based on one fullerene derivative, it is advantageous if nano-mesoscopic materials (structures) of various dimensions (0 to 3 dimensions) can be produced arbitrarily.

  Accordingly, an object of the present invention is to provide a fullerene derivative preferable for designing a novel nano-mesoscopic material having various dimensions and a method for producing the fullerene derivative. A further object of the present invention is to provide a novel nano-mesoscopic material having various dimensions using such a fullerene derivative and a method for producing the same.

The fullerene derivative represented by the formula (1) according to the present invention includes a fullerene moiety (A), an alkyl chain moiety (B) containing at least one alkyl substituent with or without a substituent, and the fullerene moiety (A). And a binding site (R) that binds the alkyl chain site (B),
Here, X is a hydrogen atom or a methyl group, the binding site (R) has at least one benzene ring, and the alkyl chain site (B) is maintained on a substantially planar surface. Each of said at least one alkyl substituent at chain site (B) extends in substantially the same direction, thereby achieving the above objective.

The fullerene moiety (A) may include a fullerene selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ .

  The alkyl chain moiety (B) can have three alkyl substituents.

The at least one alkyl substituent is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), N may be an integer greater than or equal to 2.

  The n may be 12-20.

The substituent may be selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).

Said binding site (R) may be selected from the group consisting of benzene, naphthalene, anthracene, and pyrene, with or without additional substituent Y, as shown in formula (3).

The method for producing a fullerene derivative according to the present invention comprises the step of reacting a binding member selected from the group consisting of formula (4), fullerene and N-methylglycine represented by formula (5),
Here, R ₁ is an alkyl substituent with or without a substituent, R ₂ and R ₃ are each a hydrogen atom or an alkyl group with or without a substituent, and X is a hydrogen It is an atom or a methyl group, Y is a hydrogen atom or a further substituent, thereby achieving the above objective.

The fullerene may be selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ .

The alkyl substituents of R ₁ , R ₂ and R ₃ are each composed of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ). Selected from the group, where n may be an integer greater than or equal to two.

  The n may be 12-20.

The substituent may be selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).

  The reacting step may be refluxed in toluene at a temperature of 110 ° C. for 12-24 hours.

The nano-mesoscopic material comprising a plurality of fullerene derivatives according to the present invention is such that each of the plurality of fullerene derivatives has at least one alkyl substitution with or without a fullerene moiety (A) represented by formula (1) An alkyl chain site (B) containing a group, and a binding site (R) that binds the fullerene site (A) and the alkyl chain site (B),
Here, X is a hydrogen atom or a methyl group, the binding site (R) has at least one benzene ring, and the alkyl chain site (B) is maintained on a substantially planar surface. Each of the at least one alkyl substituent in the chain part (B) extends in substantially the same direction, and the plurality of fullerene derivatives are composed of a plurality of pairs of fullerene derivatives, Each of the fullerene derivatives is alternately arranged so that one fullerene part (A) and the other alkyl chain part (B) are bonded to each other, thereby achieving the above object.

The fullerene moiety (A) may include a fullerene selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ .

  The alkyl chain moiety (B) can have three alkyl substituents.

The at least one alkyl substituent is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), N may be an integer greater than or equal to 2.

  The n may be 12-20.

The substituent may be selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).

Said binding site (R) may be selected from the group consisting of benzene, naphthalene, anthracene, and pyrene, with or without additional substituent Y, as shown in formula (3).

  The nano-mesoscopic material is a hollow sphere, and the plurality of pairs of fullerene derivatives may be positioned such that a wall thickness direction of the hollow spheres matches a longitudinal direction of each of the plurality of pairs of fullerene derivatives. .

  The nano-mesoscopic material is a fiber material, and the plurality of pairs of fullerene derivatives may be positioned such that the longitudinal direction of the fiber material and the longitudinal directions of the plurality of pairs of fullerene derivatives are orthogonal to each other.

  The nano-mesoscopic material may be a disc material, and the plurality of pairs of fullerene derivatives may be positioned such that a thickness direction of the disc material matches a longitudinal direction of the plurality of pairs of fullerene derivatives.

  The nano-mesoscopic material may be a flower material that is a random collection of the disk material.

The nano-mesoscopic material may be a cone material, and the plurality of pairs of fullerene derivatives may be positioned such that a wall thickness direction of the cone material matches a longitudinal direction of each of the plurality of pairs of fullerene derivatives. .

  The tapered end of the cone material may have a hole.

In the method for producing a nano-mesoscopic material comprising a plurality of fullerene derivatives according to the present invention, each of the plurality of fullerene derivatives has at least a fullerene moiety (A) represented by formula (1) and a substituent. An alkyl chain site (B) containing one alkyl substituent, and a binding site (R) that binds the fullerene site (A) and the alkyl chain site (B),
Here, X is a hydrogen atom or a methyl group, the binding site (R) has at least one benzene ring, and the alkyl chain site (B) is maintained on a substantially planar surface. Each of the at least one alkyl substituent in the chain part (B) extends in substantially the same direction, and is a step of adding a predetermined solution to a plurality of fullerene derivatives and heating, wherein the predetermined solution Includes a step of being a poor solvent for the plurality of fullerene derivatives and having a polarity higher than that of tetrahydrofuran, and holding the reaction solution obtained in the heating step. Achieve the goal.

The fullerene moiety (A) may include a fullerene selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ .

  The alkyl chain moiety (B) can have three alkyl substituents.

The at least one alkyl substituent is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), N may be an integer greater than or equal to 2.

  The n may be 12-20.

The substituent may be selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).

Said binding site (R) may be selected from the group consisting of benzene, naphthalene, anthracene, and pyrene, represented by formula (3), with or without further substituents.

  The heating step may be held at a temperature of 60 ° C. for 2 hours.

  When the nano mesoscopic material is a hollow sphere, the predetermined solution is a 2-propanol solution, and when the nano mesoscopic material is a fiber material, the predetermined solution is a linear m-alkyl alcohol ( M represents carbon number, and 3 ≦ m ≦ 5), and when the nano-mesoscopic material is a disk material, the predetermined solution is 1,4-dioxane, and the nano-mesoscopic material is corn. When it is a material, the predetermined solution may be a tetrahydrofuran solution.

  When the nano-mesoscopic material is a hollow sphere, the 2-propanol solution is a mixed solution of 2-propanol and toluene, and the ratio of the mixed solution is 0% to 50% of the toluene in the 2-propanol. It can be.

  When the nano-mesoscopic material is a fiber material, the linear m-alkyl alcohol may be 1-propanol.

  When the nano-mesoscopic material is a corn material, the tetrahydrofuran solution is water or a mixed solution of methanol and tetrahydrofuran, and the ratio of the mixed solution is 20% to 50% of the water or methanol in the tetrahydrofuran. possible.

The holding step may hold the reaction solution at room temperature for 12 to 24 hours.
In the holding step, when the nano-mesoscopic material is a flower material, the predetermined solution is 1,4-dioxane, and the reaction solution may be held at a temperature of 5 ° C. or less for 12 to 24 hours.

  When the nano-mesoscopic material is a hollow sphere and the 2-propanol solution is a mixed solution of 2-propanol and toluene, the reaction solution is held at a temperature of 5 ° C. or lower for 12 to 24 hours, and subjected to ultrasonic treatment. The method may further include the step of:

  The device according to the invention may comprise the above materials.

In the fullerene derivative according to the present invention, the alkyl chain moiety can be kept flat with respect to the spherical fullerene moiety via the binding moiety. As a result, there is a difference (balance) between the collective force due to the π-π interaction of the fullerene moiety composed of sp ² carbon and the collective force due to the hydrophobic interaction of the alkyl chain moiety composed of sp ³ carbon. By utilizing such a difference, the organization of molecules can be promoted, and various novel nano-mesoscopic materials can be constructed.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
(Embodiment 1)
FIG. 1 is a schematic view of a fullerene derivative according to the present invention.
The fullerene derivative according to the present invention has a structure represented by the formula (1).

  The fullerene derivative of the present invention includes a fullerene moiety (A), an alkyl chain moiety (B), and a binding site (R) that binds the fullerene moiety (A) and the alkyl chain moiety (B).

The fullerene moiety (A) includes fullerene and a nitrogen-containing five-membered ring portion. The fullerene is selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ . Preferably, the fullerene is C _60. This is because C ₆₀ has extremely high I _h target properties, is the most stable and inexpensive, and is easy to handle and can be easily chemically modified. The nitrogen-containing five-membered ring portion functions to bond a binding site (R) described later and fullerene. X of the nitrogen-containing five-membered ring part is hydrogen or a methyl group.

The fullerene moiety (A) has a collective force due to the π-π interaction of fullerene composed of sp ² carbon.
The alkyl chain part (B) contains 1 to 3 alkyl substituents with or without substituents.

Structure 110 in FIG. 1 shows the case where the alkyl substituent is 1, structure 120 shows the case where the alkyl substituent is 2, and structure 130 shows the case where the alkyl substituent is 3. Each of the 1-3 alkyl substituents extends in substantially the same direction. Although the same direction is a horizontal direction, for example, it is not limited to this. Note that “substantially the same” means that depending on the skeleton of the alkyl substituent, the longitudinal directions of the respective alkyl substituents do not completely coincide, but extend in the same direction as a whole. Such alkyl substituents consist of sp ³ carbons and have a collective force due to hydrophobic interactions.

The alkyl chain moiety (B) preferably has three alkyl substituents (structure 130). This is because the structure of the fullerene derivative as a whole is stable when considering the diameter of the fullerene moiety (A) and the width of the alkyl chain moiety (B), and it is easy to produce nano-mesoscopic materials (form an organized structure). It is.
Alkyl substituent having 1 to 3 are each alkyl _{(C n H 2n + 1)} , alkoxyl _{(OC n H 2n + 1)} , and is selected from the group consisting of thioalkyl _{(SC n H 2n + 1)} . here,
n is an integer of 2 or more. Preferably, n is 12-20. When n is less than 12, the collective force of the molecules at the alkyl chain site (B) decreases, so that it becomes difficult to form an organized structure. On the other hand, if n exceeds 20, the collective force of the molecules in the alkyl chain part (B) increases, but the balance with the collective force of the fullerene part (A) is not maintained, and it becomes difficult to form an organized structure. . In addition, when the alkyl chain part (B) has two or more alkyl substituents (structure 120 or structure 130), they may be the same or different.

Each of 1 to 3 alkyl substituents may have a small bulky substituent 150 or 170 (FIG. 1) at each intermediate site or each terminal site. In the case of a bulky substituent, the organized structure may be disrupted. When the alkyl substituent has a substituent at an intermediate site as shown in the structure 140 of FIG. 1, the substituent 150 is preferably a diacetylene group, an azobenzene group, and a stilbene group represented by the formula (2). Selected from the group consisting of Since the diacetylene group forms a diacetylene polymer by polymerization, the alkyl chain site (B) may have conductivity. Since each of the azobenzene group and the stilbenzene group can be photoisomerized, the morphology of the nano-mesoscopic material after formation of the structured structure can be changed by light.

  When the alkyl substituent has a substituent at the terminal site as shown in the structure 160 of FIG. 1, the substituent 170 capable of molecular recognition or hydrogen bonding is preferred. With such a substituent, a host-guest reaction in the nano-mesoscopic material after formation of the structured structure can be expected. Such substituents 170 can be, for example, carboxylic acids, amines, amino acids, alcohols, and boronic acids.

The binding site (R) has at least one benzene ring and maintains the alkyl chain site (B) substantially in a plane. The binding site (R) is preferably selected from the group consisting of benzene, naphthalene, anthracene and pyrene shown in formula (3), with or without further substituent Y. With these binding sites (R), the alkyl chain site (B) is maintained substantially on a plane, and the respective alkyl substituents of the alkyl chain site (B) are oriented in substantially the same direction. be able to. In addition, substantially “planar” means that the alkyl substituents of the alkyl chain part (B) are not completely arranged on one plane, but are arranged on a plane as a whole. Intended. Further substituents Y can be, for example, methyl, alcohol and amine, or are hydrogen atoms.

  As described above, the fullerene derivative according to the present invention may have a difference (balance) between the aggregation force of the fullerene moiety (A) and the aggregation force of the alkyl chain moiety (B). As will be described later, by utilizing such a difference, it is a novel fullerene derivative that can promote the organization of molecules and can construct various novel nano-mesoscopic materials.

Next, the manufacturing method of the fullerene derivative by this invention is demonstrated.
The production method of a fullerene derivative according to the present invention includes a step of reacting a binding member selected from the group consisting of formula (4), fullerene and N-methylglycine represented by formula (5).
Where R ₁ is an alkyl substituent with or without a substituent, R ₂ and R ₃
Are each a hydrogen atom or an alkyl substituent with or without a substituent, X is a hydrogen atom or a methyl group, and Y is a hydrogen atom or a further substituent. The connection positions of R ₁ , R ₂ and R ₃ are arbitrary, but are positioned so as to be horizontal.

The alkyl substituents for R ₁ , R ₂ and R ₃ are each a group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ). Selected from. Here, n is an integer of 2 or more. Preferably, n is 12-20. The alkyl substituents for R ₁ , R ₂ and R ₃ may be the same or different.

Each of the alkyl substituents of R ₁ , R ₂ and R ₃ may have a small bulky substituent at each intermediate site or each terminal site. In the case of a bulky substituent, the organized structure may be disrupted. When the alkyl substituent has a substituent at an intermediate site, the substituent is preferably selected from the group consisting of a diacetylene group, an azobenzene group, and a stilbene group shown in Formula (2). When the alkyl substituent has a substituent at the terminal site, a substituent capable of molecular recognition or hydrogen bonding is preferred. Such substituents can be, for example, carboxylic acids, amines, amino acids, alcohols, and boronic acids. The binding element represented by the formula (4) may be synthesized or a commercially available product may be used.

The fullerene is selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₆ .
The reaction step is more specifically refluxed at a temperature of 110 ° C. in toluene as a solvent for 12 to 24 hours (including 12 hours and 24 hours). The reactant obtained in the reacting step may be cooled and chromatographed using toluene and then toluene / n-hexane (mixed 1: 1) as eluent.

(Embodiment 2)
Next, the nano mesoscopic material using the fullerene derivative according to the present invention will be described.
FIG. 2 is a schematic diagram of various nano-mesoscopic materials using the fullerene derivative according to the present invention.
Various nano-mesoscopic materials according to the present invention include a plurality of fullerene derivatives 200. The fullerene derivative 200 is the fullerene derivative described in Embodiment 1, and includes a fullerene portion 210 and an alkyl chain portion 220. In the fullerene derivative 200 shown in FIG. 2, the binding site is omitted for simplicity. The nano mesoscopic material of the present invention can take various structures ranging from 0 to 3 dimensions using a plurality of pairs of fullerene derivatives 230. As shown in the figure, the pair of fullerene derivatives 230 are arranged so that the fullerene derivatives 200 are alternately arranged, that is, one fullerene portion 210 and the other alkyl chain portion 220 are bonded to each other. Such an alternating arrangement is generated in a self-organized manner due to the difference (balance) between the collective force of the fullerene site 210 and the collective force of the alkyl chain site 220. More specifically, such an alternating sequence occurs at a relatively low temperature, and such an alternating sequence decomposes at a relatively high temperature, and the fullerene derivative 200 may exist alone. Since such a feature is reversible, it can be appropriately regenerated and decomposed, which is extremely advantageous in design.

Next, the manufacturing method of various nano mesoscopic materials by this invention is demonstrated.
FIG. 3 is a diagram illustrating steps for manufacturing various nano-mesoscopic materials using the fullerene derivative according to the present invention.
Step S310: A predetermined solution is added to the fullerene derivative 200 and heated. The predetermined solution is a poor solvent for the fullerene derivative 200 and has a polarity higher than that of tetrahydrofuran. The heating step is preferably performed at a temperature of 60 ° C. for 2 hours.
Step S320: The reaction solution obtained in step S310 is held.
Various nano-mesoscopic materials can be obtained from one kind of fullerene derivative 200 depending on selection of a predetermined solution and conditions for holding the reaction solution.
Prior to step S310, the fullerene derivative 200 may be dissolved in a solvent (for example, chloroform), and then the solvent may be dried to produce a cast film of the fullerene derivative 200. Thereby, progress of a heating reaction can be promoted.

Next, various nano mesoscopic materials composed of a plurality of pairs of fullerene derivatives 230 and methods for producing the same will be described in detail.
<1.0-dimensional nano-mesoscopic materials>
Refer to FIG. 2 again. The hollow sphere 240 is a zero-dimensional nano mesoscopic material. As shown in the structure A, the fullerene derivatives 200 are arranged so that the direction of the wall thickness of the hollow sphere 240 matches the longitudinal direction of the pair of fullerene derivatives 230. The wall thickness of the hollow sphere 240 may correspond to an integral multiple of the pair of fullerene derivatives 230 in the longitudinal direction.

  Since the wall thickness of the hollow sphere 240 corresponds to an integral multiple of the length of the fullerene derivative 200 in the longitudinal direction, the chain length of the alkyl chain portion 220 is changed, or the pair of fullerene derivatives 230 is formed into a multilayer structure. By doing so, the wall thickness can be arbitrarily controlled. This is advantageous in material design. Moreover, since the size of the hollow sphere 240 is in the range of nanometer order to micrometer order depending on manufacturing conditions, the hollow size can be variably controlled.

  Such a hollow sphere 240 is applied to an application using a hollow space or the hollow sphere itself. As an application using the hollow space, there is one in which various materials are included in the hollow space. More specifically, when the inclusion is a magnetic material, a new material is expected due to the interaction between the photoresponsiveness of the fullerene derivative 200 and magnetism. When the inclusion is a drug, it can function as a drug delivery. In particular, since the structure of the hollow sphere 240 can be changed with respect to temperature, it is possible to decompose the hollow sphere 240 at the affected area and apply the medicine directly to the affected area. On the other hand, an application using the hollow sphere itself includes a nanometer or micrometer size component using the conductivity of the fullerene portion 210 of the fullerene derivative 200. More specifically, it can be a nanometer-sized conductive ball, and wiring can be connected to the conductive ball.

The hollow spheres 240 according to the present invention are very close to a perfect circle and have excellent monodispersity as compared with conventional sphere materials, so that reliability and yield can be improved in applications.
FIG. 4 is a diagram showing detailed steps for producing various nano-mesoscopic materials using fullerene derivatives according to the present invention.

The steps for manufacturing the hollow sphere 240 according to the present invention will be described in detail.
Step S310A: A 2-propanol solution is added as a predetermined solution to the fullerene derivative 200 and heated. Preferably, a mixed solution of 2-propanol and toluene is used as the predetermined solution. The ratio of the mixed solution is 0% to 50% of toluene in 2propanol. This is because the use of the mixed solution increases the affinity with the fullerene portion 210 and facilitates the formation of a structure having a curvature.
Step S320A: The reaction solution obtained in Step S310A is held at room temperature (20 ° C. to 25 ° C.) for 12 hours to 24 hours.

  Thereby, the hollow sphere 240 shown in FIG. 2 is obtained in a self-organized manner. Furthermore, following step S320A, ultrasonic treatment may be performed while the reaction solution is held at a temperature of 5 ° C. or lower for 12 to 24 hours. Thereby, the particle diameter of the obtained hollow sphere 240 grows, and a microsphere-sized hollow sphere is obtained. When the ultrasonic treatment is further continued, the grown hollow spheres can be combined to form a fiber material.

<2.1-dimensional nano-mesoscopic materials>
Refer to FIG. 2 again. The fiber material 250 is a one-dimensional nano mesoscopic material. As shown in the structure A, the fullerene derivative 200 can be arranged so that the longitudinal direction of the fiber material 250 and the longitudinal direction of the pair of fullerene derivatives 230 are orthogonal to each other. That is, the width and thickness of the fiber material 250 correspond to the length in the longitudinal direction of the pair of fullerene derivatives 230 (or an integral multiple of the length) and the thickness of the fullerene portion 210 or the alkyl chain portion 220, respectively. .

  Since such a fiber material 250 is an aggregate of fullerene derivatives 200, the fiber material 250 has flexibility, can cope with a complicated shape, and can overcome the disadvantages of conventional carbon nanotubes. Further, the fiber material 250 may be used as a conductive wire by utilizing the conductivity of the fullerene portion 210 of the fullerene derivative 200.

Referring again to FIG. 4, the steps for manufacturing the fiber material 250 will be described in detail.
Step S310B: A linear m-alkyl alcohol (where m represents the number of carbon atoms and 3 ≦ m ≦ 5) is added to the fullerene derivative 200 as a predetermined solution and heated. Preferably, 1-propanol is used as the predetermined solution.
Step S320A: The reaction solution obtained in Step S310B is held at room temperature (20 ° C. to 25 ° C.) for 12 hours to 24 hours.
Thereby, the fiber material 250 shown in FIG. 2 is obtained in a self-organized manner.

<3. Two-dimensional nano-mesoscopic materials>
Refer to FIG. 2 again. The disk material 260 is a two-dimensional nano mesoscopic material. As shown in Structure B, the fullerene derivative 200 can be arranged so that the thickness direction of the disk material 260 and the longitudinal direction of the pair of fullerene derivatives 230 coincide. That is, the thickness of the disk material 260 corresponds to the length in the longitudinal direction of the pair of fullerene derivatives 230 (or an integral multiple of the length).
In such a disk material 260, the conductive fullerene sites 210 are located at both ends in the thickness direction of the disk material 260, and the insulating alkyl chain sites 220 are located inside the disk material 260. It can be used as a capacitor or a capacitor. Furthermore, it can also be expected as a memory element using local photopolymerization using a SNOM / STM probe.

Referring again to FIG. 4, the steps for manufacturing the disk material 260 will be described in detail.
Step S310C: A solvent having a slight solubility in the fullerene derivative 200 is added to the fullerene derivative 200 as a predetermined solution even at room temperature (20 ° C. to 25 ° C.) and heated. Specifically, 1,4-dioxane is preferable as the predetermined solution.
Step S320A: The reaction solution obtained in Step S310C is held at room temperature (20 ° C. to 25 ° C.) for 12 hours to 24 hours.
Thereby, the disk material 260 shown in FIG. 2 is obtained in a self-organized manner. Subsequent to step S320A, the reaction solution is spin coated or dip coated on the substrate to change the thickness of the disk material 260 from a single layer (that is, a single layer state of the pair of fullerene derivatives 230) to a multilayer (that is, a pair of layers). Of the fullerene derivative 230).

<3D nano-mesoscopic materials>
Refer to FIG. 2 again. The cone material 270 is a three-dimensional nano mesoscopic material. As shown in structure A, the fullerene derivative 200 can be arranged so that the direction of the wall thickness of the cone material 270 matches the longitudinal direction of the pair of fullerene derivatives 230. That is, the wall thickness of the cone material 270 corresponds to the length in the longitudinal direction of the pair of fullerene derivatives 230 (or an integral multiple of the length). The tapered end of the cone material 270 has a hole. The pore size is on the nanometer level.
Such a cone material 270 can adsorb a relatively large substance such as a protein in a space in the cone, and can have a sensing function. The cone material 270 of the present invention is in the nanometer to micrometer range, and can cover the range that conventional carbon nanohorns could not cover.

Referring again to FIG. 4, the steps for manufacturing the cone material 270 will be described in detail.
Step S310D: A tetrahydrofuran solution is added to the fullerene derivative 200 as a predetermined solution and heated. The tetrahydrofuran solution can disperse the fullerene derivative 200 as a monomer. Such a tetrahydrofuran solution may be a mixed solution of tetrahydrofuran and a polar solvent. Preferably, it may be a mixed solution of water or methanol and tetrahydrofuran. The ratio of the mixed solution is 20% to 50% of water or methanol in tetrahydrofuran.
Step S320A: The reaction solution obtained in Step S310D is held at room temperature (20 ° C. to 25 ° C.) for 12 hours to 24 hours.
Thereby, the cone material 270 shown in FIG. 2 is obtained in a self-organizing manner.

<3D nano-mesoscopic materials>
Refer to FIG. 2 again. Flower material 280 is another three-dimensional nano-mesoscopic material. The flower material 280 is an arbitrary (random) collection of a plurality of disk materials 260. Therefore, in the flower material 280, as shown in the structure B, the fullerene sites 210 face each other in the thickness direction of the flower material 280, and the fullerene derivatives 200 are alternately arranged.

  Such a flower material 280 has a larger specific surface area than the hollow sphere 240, the fiber material 250, the disk material 260, and the cone material 270 described above, and thus is effective for a catalyst carrier, a fuel cell, and a hydrogen storage material. The flower material 280 is used as a decorative object at the nanometer level. For example, when the flower material 280 is mixed with a fluorescent material, light can be emitted extremely vividly.

Referring again to FIG. 4, the steps for manufacturing flower material 280 will be described in detail.
Step S310C: A solvent having a slight solubility in the fullerene derivative 200 is added to the fullerene derivative 200 as a predetermined solution even at room temperature (20 ° C. to 25 ° C.) and heated. Specifically, 1,4-dioxane is preferable as the predetermined solution. This step S310C is the same as step S310C for manufacturing the disk material 260.
Step S320B: The reaction solution obtained in Step S310C is held at a temperature of 5 ° C. or lower for 12 hours to 24 hours.
Thereby, the flower material 280 shown in FIG. 2 is obtained in a self-organized manner. Flower material 28
0 uses 1,4-dioxane similar to the disk material 260 as the predetermined solution in step S310 (FIG. 3), but only changes the holding temperature in step S320 (FIG. 3) from that of the disk material 260. Different dimensions of nano-mesoscopic materials are obtained.

  As described above, various nano-mesoscopic materials ranging from 0 to 3 dimensions can be easily produced using the fullerene derivative 200 according to the present invention. The obtained nano-mesoscopic material utilizes the difference between the collective force of the fullerene moiety 210 and the collective force of the alkyl chain moiety 220 of the fullerene derivative 200, and thus can be reconstructed even once decomposed (reversible). . Thereby, since decomposition | disassembly and reproduction | regeneration can be operated according to a condition, it may be advantageous.

  The present invention will now be described in detail using specific examples, but it should be noted that the present invention is not limited to these examples.

3,4,5-trihydroxybenzaldehyde (430 mg, 2.5 mmol), hexadecyl bromide (4.58 g, 15 mmol), K ₂ CO ₃ (1.04 g, 7.5 mmol), KI (25 mg), , N, N-dimethylformamide (DMF) 15 mL was stirred at 70 ° C. for 14 hours. The resulting reaction was cooled to room temperature and mixed with water. The resulting water soluble upper layer was extracted with CHCl ₃ . The organic layer was treated with brine and dried over Na ₂ SO ₄ . The solvent was removed under reduced pressure, and purification was performed using column chromatography (silica gel, CHCl ₃ / n-hexane = 2/3 as an eluent). It was then recrystallized from CHCl ₃ / MeOH and the resulting product (white powder, 2.05 g, 2.48 mmol) was analyzed.

The resulting product was dissolved in deuterated chloroform and identified using nuclear magnetic resonance (NMR spectroscopy). The apparatus used was an FT-NMR apparatus (JEOL model AL300, JEOL, Japan). An identification result is shown.
¹ H NMR (300 MHz, CDCl ₃ , 20 ° C., TMS): δ 9.83 (s, 1H), 7.08 (s, 2H), 4.06 (t, 2H, J = 6.6 Hz). 03 (t, 4H, J = 6.4 Hz), 1.87-1.70 (m, 6H), 1.47-1.26 (m, 78H), 0.88 (t, 9H, J = 6) .8Hz)

The product was then subjected to fast atom bombardment mass spectrometry (FABMS) (JMS-700, JEOL, Japan). An identification result is shown.
FABMS: 827.9 (C ₅₅ H ₁₀₂ O ₄ theoretical value; 826.8)
Composition analysis: C79.64% (C ₅₅ H ₁₀₂ theoretical value of O ₄ of C; 79.84%), H12.48% ( theoretical value for C ₅₅ H ₁₀₂ O ₄ of H; 12.34%)

  From the above results, it was confirmed that the obtained product was 3,4,5-trihexadecyloxybenzaldehyde.

Synthesized 3,4,5-trihexadecyloxybenzaldehyde (827 mg, 1.0 mmol), C ₆₀ (720 mg, 1.0 mmol), N-methylglycine (445 mg, 5.0 mmol), and toluene (800 mL) Were mixed and refluxed for 21 hours. After cooling, the reaction was chromatographed on silica gel using toluene and then toluene / n-hexane (1/1) as the eluent. The reaction product was recrystallized from 1,4-dioxane to obtain a synthetic product (468 mg, 0.297 mmol, 29.7%).

Similarly, nuclear magnetic resonance was performed on the synthesized product. Results are shown.
¹ H NMR (300 MHz, CDCl ₃ , 20 ° C., TMS); δ 7.24-6.80 (br, 2H), 4.98 (d, 1H, J = 9.2 Hz), 4.81 (s, 1H ), 4.24 (d, 1H, J = 9.4 Hz), 3.95 (m, 6H), 2.85 (s, 3H), 1.69 (m, 6H), 1.41-1. 24 (m, 78H), 0.88 (t, 9H, J = 7.1 Hz)
¹³ C NMR (75 MHz, CDCl ₃ , 20 ° C., TMS); δ 156.2, 154.
15, 153.97, 153.5, 147.37, 147.36, 147.008, 146.52, 146.37, 146.26, 146.20, 146.12, 146.00, 145.98, 145.81, 145.59, 145.55, 145.37, 145.31, 145.28, 145.21, 144.74, 144.73, 144.43, 143.20, 143.02, 142. 74, 142.63, 142.61, 142.27, 142.19, 142.15, 142.11, 142.05, 141.91, 141.86, 141.71, 141.62, 140.24, 140.13, 139.70, 138.54, 136.61, 136.22, 135.79, 131.88, 83.74, 73.30, 70.07, 69.43 68.98, 40.11, 31.96, 30.33, 29.75, 29.70, 29.64, 29.47, 29.40, 29.32, 26.13, 26.08, 22. 72, 14.13, 14.11.

High resolution mass spectrometry and composition analysis were performed on the synthesized product using a laser ion time-of-flight mass spectrometer MALDI TOF-MS (Voyager-DE STR, Applied Biosystem, USA). An identification result is shown.
MALDI-TOF-MS (matrix, 2-amino-5 nitropyridine); 1174.96 (C ₁₁₇ H ₁₀₇ O ₃ N theoretical value; 1174.83)
Composition analysis: C88.68% (theoretical value for _{C 117 H 107 O 3 N ·} 0.5H 2 O of C; 88.71%), H7.02% (C 117 H 107 O 3 N · 0.5H 2 Theoretical value of H in O; 6.87%), N 0.85% (theoretical value of N in C ₁₁₇ H ₁₀₇ O ₃ N · 0.5H ₂ O; 0.88%)

Furthermore, the infrared absorption spectrum was measured about the obtained synthetic | combination product using the Fourier-transform infrared spectrophotometer (Nicolet Nexus670, Thermo Electron, USA). An identification result is shown.
IR (KBr, cm ⁻¹ ) 2918.8, 2850.3, 2777.0, 1587.2, 114.7

Ultraviolet / visible absorption spectrum measurement was performed using a UV-VIS-NIR spectrometer (V-570, JASCO, USA). An identification result is shown.
UV-vis (n-hexane, 1.0 × 10 ⁻⁵ M); λ _max (ε, mol ⁻¹ dm ³ cm ⁻¹ ) = 210 (186605), 254.5 (130666), 309 (43051), 430 (5017), 701.5 (461)

From the above, it was confirmed that the obtained synthetic product was a fullerene derivative C ₆₀ Ph3,4,5O ₃ C ₁₆ (hereinafter simply referred to as a fullerene derivative). The results are summarized in equation (6).

  The fullerene derivative obtained in Example 1 was dissolved in 1 mL (4.0 mM) of a chloroform solution, and only the solvent was evaporated to prepare a cast film. Next, 2-propanol was added to the cast film and heated at 60 ° C. for 2 hours (S310 in FIG. 3). Next, the mixture was cooled to room temperature and held for 24 hours (S320 in FIG. 3), and an organized structure (hereinafter simply referred to as object (I)) by a fullerene derivative was produced.

The obtained cast film was subjected to structural analysis using an X-ray diffractometer (RINT Ultimate III, Rigaku, Japan). The result by X-ray diffraction is shown in FIG. 5 and will be described later.
Next, the scanning film was subjected to differential scanning calorimetry (DST) and infrared absorption spectrum measurement, and the behavior of the alkyl chain due to heat was examined. A differential scanning calorimeter (DSC 6220, SII, USA) was used for DST, and a Fourier transform infrared spectrophotometer (Nicolet Nexus 670, Thermo Electron, USA) was used for the infrared absorption spectrum. The results are shown in FIG. 6 and FIG.

The obtained object (I) was observed with a transmission electron microscope TEM (JEM-1010, JEOL, Japan). Observation was performed at an acceleration voltage of 100 kV at room temperature. The sample for observation was prepared by dropping a solution containing the object (I) onto a copper grid coated with a carbon film and drying it under high vacuum. The results are shown in FIGS. 8A and 8B and will be described later.
Further, the particle size distribution of the object (I) was measured. The results are shown in FIG.
Next, the object (I) was cooled to 5 ° C., and the structure was observed with a scanning electron microscope SEM (S-4800, Hitachi, Japan). The observation was performed at an acceleration voltage of 5 to 10 kV. The sample for observation was prepared by applying object (I) to a silicon (100) substrate and coating a platinum film to prevent charge-up. Note that ion sputtering (E-1030, Hitachi, Japan) was used for coating the platinum film. The observation results are shown in FIG.

Since Example 3 is the same as Example 2 except that a mixed solution of 2-propanol and toluene (mixing ratio 1: 1) is used instead of 2-propanol, the description thereof is omitted. Similar to Example 2, the observation results by SEM and TEM of the obtained organized structure (hereinafter simply referred to as object (II)) are shown in FIGS. 10A and 10B, respectively, and will be described later.
Furthermore, it observed in detail using the high-resolution transmission electron microscope HR-TEM (JEM-2100F, JEOL, Japan). The observation was performed at room temperature with an acceleration voltage of 200 kV. The sample for observation was prepared by dropping a solution containing the object (II) onto a copper grid coated with a carbon film and drying it under high vacuum in the same manner as in TEM. The observation results are shown in FIG. 11 and will be described later.
As in Example 2, the object (II) was cooled to 5 ° C., and the structure was observed with SEM and TEM. The results are shown in FIGS. 10C and 10D, respectively, and will be described later.
Furthermore, the object (II) was cooled to 5 ° C. and subjected to ultrasonic treatment. The object (II) after the ultrasonic treatment was observed with an SEM. The results are shown in FIGS. 12A and 12B and will be described later.

  Since Example 4 is the same as Example 2 except that 1-propanol is used instead of 2 propanol, the description thereof is omitted. The observation results of the obtained structured structure (hereinafter simply referred to as object (III)) by SEM and TEM are shown in FIGS. 13A to 13C and will be described later.

Since Example 5 is the same as Example 2 except that 1,4-dioxane is used instead of 2-propanol, the description thereof is omitted. The observation result by SEM of the resulting organized structure (hereinafter simply referred to as object (IV)) is shown in FIG. 14 and will be described later.
The surface morphology of the object (IV) was observed using an atomic force microscope AFM (E-Sweep, SII, Japan). Observation was performed in tapping mode. A sample for observation was prepared by spin-coating a 1,4-dioxane solution containing the object (IV) on a silicon (100) substrate (rotation speed r = 1200 rpm). The observation results are shown in FIG.

  Since Example 6 is the same as Example 5 except that the holding temperature is 5 ° C., description thereof is omitted. The observation result by SEM of the obtained organized structure (hereinafter simply referred to as object (V)) is shown in FIG. 16 and will be described in detail.

In Example 7, instead of 2-propanol, tetrahydrofuran (THF) and water (H ₂ O) were used.
) And the mixed solution (mixing ratio 1: 1) is the same as in Example 2, and the description thereof is omitted. The observation result by SEM and TEM of the obtained organized structure (hereinafter simply referred to as object (VI)) is shown in FIG. 17 and will be described in detail.
The experimental conditions of Examples 2 to 7 are summarized in Table 1.

FIG. 5 is a diagram showing an X-ray diffraction pattern of a cast film made of a fullerene derivative dissolved in a chloroform solution.
The X-ray diffraction pattern showed periodic clear peaks of (001), (002), (003), (004), (005) and (006). In addition, a broad peak seen in the vicinity of 2θ≈9.5 ° is a peak indicating the two-dimensionality of fullerene C ₆₀ (corresponding to a surface interval d = 0.93 nm). From the above, it is suggested that fullerene derivatives are regularly and periodically arranged in a multilayer structure in the cast film. The period (plane spacing) of the multilayer structure was found to be 4.3 nm.

  Here, the period of 4.3 nm corresponds to a length obtained by adding the size of the fullerene site to the length in the longitudinal direction of the fullerene derivative produced in Example 1. From this, in the cast film, the fullerene derivatives are arranged so as to be aligned in the respective longitudinal directions, and a pair (that is, a bilayer structure) is formed such that the fullerene sites are opposed to each other. This is suggested (a pair of fullerene derivatives 230 in FIG. 2).

FIG. 6 is a diagram showing the temperature dependence of the differential calorific value of a cast film made of a fullerene derivative dissolved in a chloroform solution.
From the figure, two endothermic peaks were observed at 26.5 ° C. and 30.6 ° C. when the temperature was changed from the low temperature side to the high temperature side. The values of enthalpy ΔH and entropy ΔS at 30.6 ° C. were calculated as ΔH = 41.6 kJmol ⁻¹ and ΔS = 136.9 kJmol ⁻¹ K ⁻¹ , respectively. This entropy value is calculated as the entropy of the phase transition of the alkyl chain (hexadecyl 3 entropy is calculated as ΔS = 92.6 kJmol ⁻¹ K ⁻¹ (the entropy per methylene is ΔS = 1.93 kJmol ⁻¹ K ^{− 1} ))) and the entropy of the fullerene site C ₆₀ (ΔS = 30-40 kJmol ⁻¹ K ⁻¹ ) showed good agreement. From these results, it was shown that the fullerene derivative was paired (that is, a bilayer structure) in the cast film.

FIG. 7 is a diagram showing the temperature dependence of the infrared absorption spectrum of a cast film made of a fullerene derivative dissolved in a chloroform solution.
As shown in the figure, the infrared absorption spectrum at 20 ° C. showed peaks due to stretching vibration of CH ₂ at 2849 cm ⁻¹ (ν _sym ) and 2918 cm ⁻¹ (ν _asym ). On the other hand, 60
In the infrared absorption spectrum at 0 ° C., the peak was found to blue shift to 2852 cm ⁻¹ and 2922 cm ⁻¹ . This also indicates that the fullerene derivative maintains a bilayer structure (a pair of fullerene derivatives 230 in FIG. 2) at low temperatures, and causes a phase transition in the alkyl chain of the fullerene derivative at high temperatures, thus eliminating the bilayer structure. It was shown that there is a nature.

FIG. 8 is a diagram showing the observation results of the object (I) by TEM and SEM.
8A and 8B are photographs taken by TEM having different magnifications. The object (I) was found to have a hollow sphere structure (0 dimension) with a diameter of about 100 nm. As shown in the SEM photograph in FIG. 8C, when the object (I) was cooled to 5 ° C., the spherical structure collapsed.

FIG. 9 is a diagram showing the particle size distribution of the object (I).
According to the method of the present invention, it was found that the object (I) having an average particle diameter of about 100 nm was obtained in a monodisperse manner. Thus, obtaining a monodispersed hollow sphere structure object very easily leads to an improvement in yield and is advantageous.

FIG. 10 is a diagram illustrating the observation result of the object (II) by TEM and SEM.
It was found from FIGS. 10A and 10B that the object (II) has a hollow sphere structure similar to that of the object (I). However, object (II) maintained the spherical structure even when cooled to 5 ° C., as shown in FIGS. 10 (C) and (D). From this, it was found that by adding toluene to 2-propanol, the spherical structure can be made temperature resistant.

FIG. 11 is a diagram illustrating an observation result of the object (II) by HR-TEM.
From the figure, the object (II) is a hollow sphere extremely close to a perfect circle, and its wall thickness was 8 to 9 nm. This wall thickness was found to correspond to two bilayers of fullerene derivatives.

FIG. 12 is a diagram showing an observation result by SEM of the object (II) subjected to low temperature / sonication.
FIG. 12A shows an observation result by SEM of the object (II) after being subjected to ultrasonic treatment at a low temperature for a relatively short time. It can be seen that the object (II) after treatment also has a hollow sphere structure, but has a particle size about 15 times that of FIG. 10 (A). That is, it has been found that the object (II) can grow grains by the processing.
FIG. 12B shows an observation result by SEM of the object (II) after being subjected to ultrasonic treatment at a low temperature for a relatively long time. From FIG. 12 (A), it was found that the grain growth further continued, and the spheres were combined to form a fiber (one-dimensional).
In this way, it is advantageous in material design that the size of the particle size (that is, the size of the hollow space) and the shape can be controlled by the temperature and processing conditions.

FIG. 13 is a diagram showing observation results of the object (III) by SEM and TEM.
FIG. 13A shows the observation result of the object (III) by SEM. It can be seen that the object (III) has a fiber-like (one-dimensional) structure. FIGS. 13B and 13C show the observation results of the object (III) by TEM. The length of the fiber-like object (III) was about 20 μm, and it was found that it did not have a nanotube-like space but a ribbon-like shape. Such an object (III) is useful as a conductive wire.

FIG. 14 is a diagram showing the observation result of the object (IV) by SEM.
As shown in FIGS. 14A and 14B, the object (IV) has a disk-like (two-dimensional) structure with a diameter of about 0.2 to 1.5 μm. For example, unlike FIG. 10, it is not a hollow sphere but a flat plate structure.

FIG. 15 is a diagram illustrating an observation result of the object (IV) by AFM.
As shown in FIG. 15, the object (IV) was found to have a thickness of about 4.4 nm. This thickness corresponds to the length in the longitudinal direction of the bilayer structure of the fullerene derivative (the pair of fullerene derivatives 230 in FIG. 2), as described with reference to FIG. This suggests that the disc-shaped object (IV) has the bilayer structure of fullerene derivatives arranged as shown in the schematic diagram of FIG.

FIG. 16 is a diagram showing the observation result of the object (V) by SEM.
It can be seen that the object (V) has a flower-like (three-dimensional) structure similar to carnation, and the object (IV) shown in FIG. It was confirmed that the object (V) can take various shapes such as buttons and carnations depending on conditions such as the cooling rate and the cooling time. The object (V) has a large specific surface area and can carry a catalyst or the like in a portion similar to a petal.

FIG. 17 is a diagram showing the observation result of the object (VI) by SEM and TEM.
The object (VI) has a cone-shaped (three-dimensional) structure of about 1 μm to 2 μm. The wall thickness of the object (VI) is about 150 nm, which is expected to be a multilayered bilayer structure. As shown in the inset (TEM photograph) in FIG. 17, the tapered end of the object (VI) has a hole with a diameter of about 60 nm. Since the size of the cavity in the cone is at the micrometer level, a relatively large substance (for example, protein) can be sensed.
The above results are summarized in Table 2.

  As described above, when the fullerene derivative according to the present invention is used, nano mesoscopic materials having various structures from 0 to 3 dimensions can be produced by simply selecting a predetermined solution and holding temperature at the time of reaction. be able to. Such nano- and mesoscopic materials are nano-parts utilizing their own conductivity (nanowires, nanoballs), applications utilizing hollow space and specific surface area (catalyst loading, substance sensing, drug delivery, magnetic / optical applications) It can be used for capacitors, capacitors and the like.

Schematic diagram of fullerene derivatives according to the present invention Schematic diagram of various nano-mesoscopic materials using fullerene derivatives according to the present invention The figure which shows the step which manufactures various nano mesoscopic materials using the fullerene derivative by this invention Diagram showing detailed steps for manufacturing various nano-mesoscopic materials using fullerene derivatives according to the present invention The figure which shows the X-ray diffraction pattern of the cast film by the fullerene derivative dissolved in the chloroform solution Diagram showing the temperature dependence of the differential calorific value of cast films made of fullerene derivatives dissolved in chloroform solution Figure showing the temperature dependence of the infrared absorption spectrum of cast films made of fullerene derivatives dissolved in chloroform solution The figure which shows the observation result by TEM and SEM of object (I) The figure which shows the particle size distribution of object (I) The figure which shows the observation result by TEM and SEM of object (II) The figure which shows the observation result by HR-TEM of object (II) The figure which shows the observation result by SEM of the object (II) by which low temperature and ultrasonic treatment were carried out The figure which shows the observation result by SEM and TEM of object (III) The figure which shows the observation result by SEM of object (IV) The figure which shows the observation result by AFM of object (IV) The figure which shows the observation result by SEM of object (V) The figure which shows the observation result by SEM and TEM of object (VI)

Explanation of symbols

110, 120, 130, 140, 160 Structure 150, 170 Substituent 200 Fullerene derivative 210 Fullerene moiety 220 Alkyl chain moiety 230 Pair of fullerene derivatives 240 Hollow sphere 250 Fiber material 260 Disc material 270 Cone material 280 Flower material

Claims (42)

A fullerene derivative represented by the formula (1):
A fullerene moiety (A);
An alkyl chain moiety (B) comprising at least one alkyl substituent with or without substituents; and
A binding site (R) that binds the fullerene site (A) and the alkyl chain site (B);
Here, X is a hydrogen atom or a methyl group,
The binding site (R) has at least one benzene ring and maintains the alkyl chain site (B) substantially planar;
The fullerene derivative, wherein each of the at least one alkyl substituent in the alkyl chain part (B) extends in substantially the same direction. The fullerene derivative according to claim 1, wherein the fullerene moiety (A) includes a fullerene selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ .   The fullerene derivative according to claim 1, wherein the alkyl chain part (B) has three alkyl substituents. The at least one alkyl substituent is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), N is an integer greater than or equal to 2, The fullerene derivative of Claim 1.   The fullerene derivative according to claim 4, wherein n is 12 to 20. The substituent is selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).
The fullerene derivative according to claim 1. The binding site (R) is selected from the group consisting of benzene, naphthalene, anthracene, and pyrene represented by formula (3), with or without additional substituent Y.
The fullerene derivative according to claim 1. A method for producing a fullerene derivative, comprising:
Reacting a binding member selected from the group consisting of formula (4), fullerene and N-methylglycine represented by formula (5),
Here, R ₁ is an alkyl substituent with or without a substituent, R ₂ and R ₃ are each a hydrogen atom or an alkyl group with or without a substituent, and X is a hydrogen A method wherein it is an atom or a methyl group and Y is a hydrogen atom or a further substituent. The fullerene, C _60, C _70, selected from the group consisting of C ₇₆ and C _84, The method of claim 8. The alkyl substituents of R ₁ , R ₂ and R ₃ are each composed of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ). 9. The method of claim 8, wherein n is an integer greater than or equal to 2, selected from the group.   The method of claim 10, wherein n is 12-20. The substituent is selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).
The method of claim 8.   The method according to claim 8, wherein the reacting is refluxed in toluene at a temperature of 110 ° C. for 12 to 24 hours. A nano-mesoscopic material comprising a plurality of fullerene derivatives,
Each of the plurality of fullerene derivatives includes a fullerene moiety (A) represented by the formula (1), an alkyl chain moiety (B) including at least one alkyl substituent having or not having a substituent, and the fullerene moiety ( A) and a binding site (R) that binds the alkyl chain site (B),
Here, X is a hydrogen atom or a methyl group, the binding site (R) has at least one benzene ring, and the alkyl chain site (B) is maintained on a substantially planar surface. Each of said at least one alkyl substituent of chain site (B) extends in substantially the same direction;
The plurality of fullerene derivatives are composed of a plurality of pairs of fullerene derivatives,
Each of the plurality of pairs of fullerene derivatives is alternately arranged so that one fullerene moiety (A) and the other alkyl chain moiety (B) are bonded to each other. The material according to claim 14, wherein the fullerene moiety (A) comprises a fullerene selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ .   15. A material according to claim 14, wherein the alkyl chain moiety (B) has three alkyl substituents. The at least one alkyl substituent is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), The material according to claim 14, wherein n is an integer of 2 or more.   The material according to claim 17, wherein n is 12-20. The substituent is selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).
The material according to claim 14. The binding site (R) is selected from the group consisting of benzene, naphthalene, anthracene, and pyrene represented by formula (3), with or without additional substituent Y.
The material according to claim 14. The nano-mesoscopic material is a hollow sphere,
The material according to claim 14, wherein the plurality of pairs of fullerene derivatives are positioned such that a direction of a wall thickness of the hollow sphere coincides with a longitudinal direction of each of the plurality of pairs of fullerene derivatives. The nano-mesoscopic material is a fiber material;
The material according to claim 14, wherein the plurality of pairs of fullerene derivatives are positioned such that a longitudinal direction of the fiber material and a longitudinal direction of each of the plurality of pairs of fullerene derivatives are orthogonal to each other. The nano-mesoscopic material is a disk material;
The material according to claim 14, wherein the plurality of pairs of fullerene derivatives are positioned such that a thickness direction of the disk material coincides with a longitudinal direction of the plurality of pairs of fullerene derivatives.   24. The material of claim 23, wherein the nano-mesoscopic material is a flower material that is a random collection of the disk material. The nano mesoscopic material is a cone material,
The material according to claim 14, wherein the plurality of pairs of fullerene derivatives are positioned such that a wall thickness direction of the cone material coincides with a longitudinal direction of each of the plurality of pairs of fullerene derivatives.   26. The material of claim 25, wherein the tapered end of the cone material has a hole. A method for producing a nano-mesoscopic material comprising a plurality of fullerene derivatives, each of the plurality of fullerene derivatives having at least one fullerene moiety (A) represented by the formula (1) and having or not having a substituent. An alkyl chain part (B) containing two alkyl substituents, and a binding part (R) that connects the fullerene part (A) and the alkyl chain part (B);
Here, X is a hydrogen atom or a methyl group, the binding site (R) has at least one benzene ring, and the alkyl chain site (B) is maintained on a substantially planar surface. Each of said at least one alkyl substituent of chain site (B) extends in substantially the same direction;
The method
Adding a predetermined solution to the plurality of fullerene derivatives and heating, wherein the predetermined solution is a poor solvent for the plurality of fullerene derivatives and has a polarity higher than that of tetrahydrofuran; and ,
Holding the reaction solution obtained in the heating step. The fullerene part (A) comprises a fullerene selected from the group consisting of C _60, C _70, C ₇₆ and C _84, The method of claim 27.   28. The method of claim 27, wherein the alkyl chain moiety (B) has three alkyl substituents. The at least one alkyl substituent is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), 28. The method of claim 27, wherein n is an integer greater than or equal to 2.   32. The method of claim 30, wherein n is 12-20. The substituent is selected from the group consisting of diacetylene, azobenzene and stilbene represented by the formula (2).
28. The method of claim 27. The binding site (R) is selected from the group consisting of benzene, naphthalene, anthracene, and pyrene represented by formula (3), with or without additional substituents.
28. The method of claim 27.   28. The method of claim 27, wherein the heating step is held at a temperature of 60 [deg.] C. for 2 hours. When the nano mesoscopic material is a hollow sphere, the predetermined solution is a 2-propanol solution, and when the nano mesoscopic material is a fiber material, the predetermined solution is a linear m-alkyl alcohol ( Where m represents the number of carbons and 3 ≦ m ≦ 5), and when the nano-mesoscopic material is a disk material, the predetermined solution is 1,4-dioxane, and the nano-mesoscopic material is corn. 28. The method of claim 27, wherein if it is a material, the predetermined solution is a tetrahydrofuran solution.   When the nano-mesoscopic material is a hollow sphere, the 2-propanol solution is a mixed solution of 2-propanol and toluene, and the ratio of the mixed solution is 0% to 50% of the toluene in the 2-propanol. 36. The method of claim 35, wherein   36. The method of claim 35, wherein the linear m-alkyl alcohol is 1-propanol when the nano-mesoscopic material is a fiber material.   When the nano-mesoscopic material is a corn material, the tetrahydrofuran solution is water or a mixed solution of methanol and tetrahydrofuran, and the ratio of the mixed solution is 20% to 50% of the water or methanol in the tetrahydrofuran. 36. The method of claim 35, wherein:   The method according to any one of claims 35 to 38, wherein the holding step holds the reaction solution at room temperature for 12 to 24 hours.   The holding step may be performed when the nano-mesoscopic material is a flower material, and the predetermined solution is 1,4-dioxane, and the reaction solution is held at a temperature of 5 ° C. or lower for 12 to 24 hours. 28. The method according to 27.   When the nano-mesoscopic material is a hollow sphere and the 2-propanol solution is a mixed solution of 2-propanol and toluene, the reaction solution is held at a temperature of 5 ° C. or lower for 12 to 24 hours, and subjected to ultrasonic treatment. 40. The method of claim 39, further comprising the step of: An element comprising the material according to claim 14.