JP5091059B2 - Self-assembled nanotubes with fullerenes on the inner and outer wall surfaces and tuned photoconductive properties - Google Patents

Description

  The present invention relates to a hexaperihexabenzobenzocorene derivative having a group having a fullerene which may include a metal in the molecule and a hexaperihexabenzobenzocorene which does not have a group having a fullerene which may include a metal. The present invention relates to a self-organized nanosize structure containing a derivative, and a photodetecting element, a photoswitching element and a photoresponsive charge transport element using the nanosize structure.

In recent years, research and development on electronic devices using organic molecules and polymer compounds such as organic EL elements, organic transistors, and organic thin-film solar cells have been actively conducted. Advantages of using an organic compound as an electronic device include reduction in the weight and flexibility of the element and simplification of the process. In particular, the development of organic thin-film solar cells has attracted a great deal of attention, coupled with recent energy issues and environmental issues such as global warming.
In organic thin film solar cells,
A. Light absorption Separation of generated electron-hole pairs (photo-induced electron transfer from electron donor molecule to acceptor molecule)
C. Electrons and holes are allowed to flow to opposite electrodes.
3 processes are required.
As a method for effectively realizing these three processes to improve the photoelectric conversion efficiency in the organic thin film solar cell, it is important to realize a structure in which an electron donor and an acceptor are phase-separated at a molecular level.

Self-assembled coaxial nanotubes comprising a compound in which hexabenzocoronene (HBC), which has already been proposed by the present inventors, and fullerene (C ₆₀ ), which is an electron acceptor, are heterojunction at the molecular layer level ( Patent Document 1) satisfies the two conditions of a nanophase separation structure of an electron donor and an acceptor and bonding of each layer in a wide area, and application research for organic solar cell development is expected in the future.

Japanese Patent Application No. 2008-52565

  The present invention relates to a novel nanosize structure capable of adjusting photoconductivity using a molecule having fullerene as an electron donor site and electron acceptor site in the same molecule, and a photoconductive material using the same. provide.

The present inventors have already reported a self-assembled nanotube comprising a compound having fullerene in the molecule (see Patent Document 1). This is a nanotube having a layered structure as shown in FIG. 1, and is composed of an HBC skeleton forming a π-stack and fullerene covering both the inner and outer surfaces of the nanotube wall. These nanotubes show remarkable photoconductivity and are expected to be applied for organic solar cell development in the future, but the photoconductivity is fixed and it is difficult to change the photoconductivity. It was.
The present inventors have introduced a nanotube material having such photoconductivity into another nanotube material, thereby systematically changing the coverage ratio of the electron-accepting group on the nanotube surface. It has been found that the photoconductivity of can be tuned (adjusted). Furthermore, the present inventors have found that, by such adjustment, nanotubes exhibiting larger photoconductive properties than self-assembled nanotubes consisting only of compounds having fullerenes in the molecule can be obtained, and the present invention has been achieved. did.

  That is, the present invention does not have a hexaperihexabenzocoronene derivative having a group having a fullerene which may contain a metal in the molecule and a group having a fullerene which may contain a metal in the molecule. A self-assembled nano-sized structure containing a hexaperihexabenzocoronene derivative, more specifically, the present invention comprises the following general formula (1),

[Wherein, R ¹ represents an alkyl group, R ² and R ³ are C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) nOR ⁴ (where R ⁴ includes a hydrogen atom, an alkyl group or a metal) R ² and R ³ may be the same or different from each other, but at least one of R ² and R ³ has a group having fullerene Cm (n is a positive group) Represents an integer, and m is a positive integer that allows Cm to form a spherical shell structure.]
A hexaperihexabenzocoronene derivative having in its molecule a group having fullerene which may contain a metal represented by the following general formula (2),

[Wherein R ⁵ represents an alkyl group, R ⁶ represents C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) nOR ⁷ (where R ⁷ represents a hydrogen atom or an alkyl group, and n represents a positive integer) Represents.]
The present invention relates to a self-assembled nano-sized structure comprising a hexaperihexabenzocoronene derivative that does not have a fullerene-containing group that may contain a metal represented by
The self-assembled nano-sized structure of the present invention has photoconductive properties, and the present invention includes a photodetecting element, an optical switching element, and an optical device using the above-described self-assembled nano-sized structure of the present invention. The present invention relates to various light-related elements such as a responsive charge transport element and an electronic component material containing at least one of these elements.

The present invention will be described in more detail as follows.
(1) A hexaperihexabenzocoronene derivative having a group having a fullerene which may include a metal in the molecule and a hexaperihexa having no group having a fullerene which may include a metal in the molecule A self-assembled nano-sized structure containing a benzocoronene derivative.
(2) The self-assembled nanosize structure according to (1), wherein the self-assembled nanosize structure is a nanotube formed by self-assembly.
(3) Good fullerenes also be encapsulating metal, wherein a C ₆₀ fullerene (1) or self-assembled nano-sized structure according to (2).
(4) A hexaperihexabenzocoronene derivative having a group having a fullerene which may encapsulate a metal in the molecule and a hexaperihexa having no group having a fullerene which may encapsulate a metal in the molecule (1) to (1) in which the mole fraction of the hexaperihexabenzobenzocorene derivative having a group having a fullerene which may contain a metal in the molecule with respect to the total number of moles of the benzocoronene derivative is 5 to 90%. 3) The self-organized nanosize structure according to any one of the above.
(5) The self-organization according to any one of (1) to (4) above, wherein the mole fraction of a hexaperihexabenzocoronene derivative having a fullerene-containing group which may include a metal in the molecule is 5 to 50%. Nano-sized structure.
(6) A hexaperihexabenzocoronene derivative having a group having a fullerene which may contain a metal in the molecule is represented by the following general formula (1),

[Wherein, R ¹ represents an alkyl group, R ² and R ³ are C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) nOR ⁴ (where R ⁴ includes a hydrogen atom, an alkyl group or a metal) R ² and R ³ may be the same or different from each other, but at least one of R ² and R ³ has a group having fullerene Cm (n is a positive group) Represents an integer, and m is a positive integer that allows Cm to form a spherical shell structure.]
The hexaperihexabenzocoronene derivative represented by the following general formula (2) is a hexaperihexabenzocoronene derivative that does not have a fullerene-containing group in the molecule.

[Wherein R ⁵ represents an alkyl group, R ⁶ represents C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) nOR ⁷ (where R ⁷ represents a hydrogen atom or an alkyl group, and n represents a positive integer) Represents.]
The self-assembled nano-sized structure according to any one of (1) to (5), which is a hexaperihexabenzocoronene derivative represented by the formula:
(7) The self-assembled nanosize structure according to (6), wherein the R ⁴ group of the general formula (1) is a methano [60] fullerenecarboxylic acid group represented by the formula (3).

(8) The self-organization according to (6) or (7), wherein R ^{1 in} general formula (1) and R ^{5 in} general formula (2) are each independently an alkyl group having 10 to 30 carbon atoms. Nano-sized structure.
(9) The hexaperihexabenzocoronene derivative represented by the general formula (1) has the following formula (4)

The self-organized nanosize structure according to any one of (6) to (8), which is a compound represented by the formula:
(10)
The hexaperihexabenzocoronene derivative represented by the general formula (2) has the following formula (5)
The self-organized nanosize structure according to any one of (6) to (9), which is a compound represented by the formula:
(11) A photodetecting element comprising the self-assembled nanosize structure according to any one of (1) to (10).
(12) An optical switching element comprising the self-organized nanosize structure according to any one of (1) to (10).
(13) A photoresponsive load transport element comprising the self-assembled nanosize structure according to any one of (1) to (10).
(14)
An electronic component material comprising at least one element according to any one of (11) to (13).

The present invention provides a nanosized photoconductive structure in which the photoconductivity of a self-assembled nanosize structure having a fullerene which may contain a metal in the molecule is adjusted. The nano-sized structure of the present invention includes a hexaperihexabenzobenzocorene derivative having a fullerene molecule that may contain a metal, and a hexaperihexabenzobenzocorene derivative that does not have a fullerene molecule that may contain a metal Nano-sized photoconductive structures with adjusted photoconductivity can be obtained by a very simple method of mixing these hexaperihexabenzocoronene (HBC) derivatives with hydrophilic and hydrophobic substituents. It has self-assembly through amphiphilic properties and π-π stacking effect by HBC, and can form supramolecular nanotubes, and also has adjusted photoconducting properties and a novel photoresponsiveness Provide a simple element material.
The nano-sized structure of the present invention is not only applied to many electronic component materials as a light detection element, a light switching element, a photoresponsive charge transport element, etc., but also has a novel function of various electronic materials using light. An element can be provided.

The hexaperihexabenzocoronene derivative having fullerene which may contain the metal of the present invention is characterized by having HBC as an electron donor and fullerene as an electron acceptor in the same molecule. Supramolecular nanotubes, which have both hydrophilic and hydrophobic portions and are formed by self-assembly of this compound in solution, have an HBC skeleton that forms a π stack. The inner surface and the outer surface are covered with fullerene (see FIG. 1).
The hexaperihexabenzocoronene derivative having a group having a fullerene which may include the metal of the present invention has a hydrophilic group such as a polyether structure represented by the general formula (1). And having a group having a fullerene which may contain a metal, and self-assemble through amphiphilicity and hydrophobic effect, and further through the joint effect of π-π stacking due to overlap of molecular planes, Any material can be used as long as it can self-assemble to form a nano-sized aggregate.

In the general formula (1), the alkyl group represented by R ¹ is, for example, linear, branched or cyclic having 1 to 30, preferably 10 to 30, more preferably 10 to 20 carbon atoms. Specific examples of preferred alkyl groups include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and the like. May be linear, branched or cyclic. In the case of an alkyl group having 10 or less carbon atoms, a bulky group such as a t-butyl group is preferable.

In the general formula (1), examples of the alkyl group represented by R ⁴ in C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OR ⁴ represented by R ² and R ³ include carbon number 1-20, preferably 1-10, more preferably 1-6 linear, branched or cyclic alkyl groups. Specific examples include, for example, methyl group, ethyl group, propyl group, Examples include isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

In the general formula (1), the group having a fullerene Cm represented by R ⁴ in C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OR ⁴ represented by R ² and R ³ is polyethylene. There is no particular limitation as long as it can be bonded to the end of the glycol chain, but fullerene Cm having a carboxyl group is preferable from the viewpoint of ease of synthesis. M in the fullerene Cm can be a positive integer with which Cm can form a spherical shell-like structure, but 30, 60, 70, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96 Is preferable, and 60 is particularly preferable. In addition, fullerenes containing metal can also be used. n is an arbitrary positive integer, but an integer of 2 or more is more preferable. Preferred examples of _{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) n OR 4 represented by R ² and ^{R 3,} for example,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) n OH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) n OCH 3
Etc., among others,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 2 OH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 3 OH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 4 OH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 2 OCH 3,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 3 OCH 3,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 4 OCH 3,
C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) ₃ OR ⁸ , [R ⁸ is a methano [60] fullerenecarboxylic acid group represented by the formula (3)]
Etc. are mentioned as a more preferable example, but of course, it is not limited to this.

  The most preferable example of the compound represented by the general formula (1) is represented by the formula (4).

  The hexaperihexabenzocoronene derivative having no fullerene-containing group which may contain the metal of the present invention has a hydrophilic group such as a polyether structure represented by the general formula (2). However, it does not have a group having a fullerene which may encapsulate a metal, and self-assembles through amphiphilicity and hydrophobic effect, and also through the joint effect of π-π stacking due to overlap of molecular planes. Any material can be used as long as it can form a nano-sized aggregate by self-assembly.

In the general formula (2), the alkyl group represented by R ⁵ is, for example, a linear, branched or cyclic group having 1 to 30 carbon atoms, preferably 10 to 30 carbon atoms, more preferably 10 to 20 carbon atoms. Specific examples of preferred alkyl groups include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and the like. May be linear, branched or cyclic. In the case of an alkyl group having 10 or less carbon atoms, a bulky group such as a t-butyl group is preferable.

In the general formula (2), the alkyl group represented by ^{R 7} in _{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) n OR 3 represented by ^{R 6,} for example, 1 carbon atoms 20, preferably 1 to 10, more preferably 1 to 6 linear, branched or cyclic alkyl groups. Specific examples include, for example, methyl group, ethyl group, propyl group, isopropyl group, Examples thereof include a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. n is an arbitrary positive integer, but an integer of 2 or more is more preferable.
Preferable specific examples of C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) nOR ⁷ represented by R ⁶ include, for example,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) nOH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) nOCH 3
Etc., among others,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 2 OH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 3 OH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 4 OH,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 2 OCH 3,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 3 OCH 3,
_{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) 4 OCH 3
These are given as more preferred examples, but of course not limited thereto.

  The most preferable example of the compound represented by the general formula (2) is represented by the formula (5).

  The molar fraction of the compound represented by the general formula (1) compound with respect to the total number of moles of the compound represented by the general formula (1) and the general formula (2) is preferably 5 to 90%, and 5 to 80%. More preferably, 5 to 50% is still more preferable (see Examples 6, 7 and 8 described later).

The compounds represented by general formula (1) and general formula (2) of the present invention can be produced by any known method or a method analogous thereto. For example, an intermediate having a group having a fullerene in the group R ² or R ³ can be produced according to Patent Document 1, and the ring can be produced according to the method described in Patent Document 1.

   As an example of the method for producing the compound represented by the general formula (1) of the present invention, for example, a specific example of the method for producing the compound represented by the above formula (4) is shown by the following reaction route. .

First, compound 1 protected with a tosyl group (Ts) is produced, and this is bromobiphenylated to give compound 2, which is acetylated to produce compound 3. Compound 3 and a biphenylacetylene derivative are reacted to produce an acetylene derivative (compound 4), and this is reacted with a tetraphenylcyclopentadienone derivative to produce a hexaphenylbenzene derivative (compound 5). The terminal acetoxy group of the obtained hexaphenylbenzene derivative 5 is hydrolyzed to a hydroxy form (compound 6), and then cyclized in the presence of a Lewis acid to obtain a compound 7 having a coronene skeleton.
The resulting compound 7 and fullerene carboxylic acid derivative (compound 8) are esterified in the presence of a condensing agent such as DCC to produce the desired compound 9 represented by the formula (4).

The compound represented by the general formula (1) of the present invention thus produced is a hexaperihexabenzobenzo having a hydrophobic group and a hydrophilic group in the side chain previously reported by the present inventors. It was found that the same behavior as that of the coronene derivative (HBC derivative) (see Patent Document 1) was obtained.
That is, a self-assembled body as schematically shown in FIG. 1 is formed in a solvent such as toluene to form a spiral ribbon structure or a tube structure.
The helical ribbon structure and the tube are formed in a ribbon-like shape having a width of 20 nm consisting of two layers by the amphiphilicity and the π-π stacking effect of the compound represented by the general formula (1) of the present invention. The body is formed, and then the ribbon is considered to spiral around. The strength of the winding at this time is considered to be adjusted by the degree of hydration of the polyethylene glycol chain in the R ² and R ³ moieties.

Examples of the compound represented by the general formula (1) of the present invention include the compound 9 represented by the above formula (4) and the compound represented by the general formula (2) as represented by the above formula (5). For the compound 13, the self-assembly in a solvent was attempted at various mixing ratios, and nano-sized structures formed by yellow to brown self-assembly were obtained.
As a result of observing the obtained precipitate with a scanning electron microscope (SEM), it was found that this structure was a uniform 20 to 22 nm nanotube. As a result of further observation with a transmission electron microscope (TEM), it was confirmed that the inner and outer surfaces of the wall with respect to the total number of moles of Compound 9 and Compound 13 were systematically covered with fullerene.

  The present inventors measured changes in photoelectric conductivity when the coverage of the nanotubes (molar fraction of compound 9) was changed from 0% to 100%, and measured the microwave conductivity by flash photolysis (FP-TRMC). ) Method. As a result, it has been clarified that when the coverage is in the range of 5-90%, the photoconductive property is as large as or greater than that of 100% coverage (that is, a nanotube composed only of Compound 9). In particular, it was clarified that the maximum value (about 12 times that when the coverage was 100%) was exhibited when the coverage was 25%. The conversion efficiency (φ) from photons to charge carriers is considered to increase as the coverage increases, but at the same time, charge recombination due to reverse electron transfer is accelerated, so the life of the charge separation state is also shortened. As a result of suppressing the charge recombination by decreasing the coverage, the photoconductive property was successfully improved.

  As described above, the present invention provides a photoconductive material comprising a nano-sized structure formed by simultaneous self-assembly, preferably a supramolecular nanotube, and the photoconductive material of the present invention comprises: The present invention provides a novel electronic material, and is applied to many electronic component materials as a light detection element, a light switching element, a photoresponsive charge transport element, and the like. The electronic component material of the present invention can be applied to, for example, a solar cell material, a light detection element material, a nanodevice such as a molecular lead, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.
In the following examples, commercially available reagents were used as they were, unless otherwise specified. Dichloromethane (CH ₂ Cl ₂ ) and bromobenzene were dried over calcium hydride (CaH ₂ ) under an argon atmosphere and distilled before use. ¹ H and ¹³ C NMR were measured using a JEOL model NM-Excalibur 500 spectrometer at 298 ° K. at 500 MHz and 125 MHz, respectively. MALDI-TOF mass spectrometry was measured using an Applied Biosystems BioSpectrometry ^™ Workstation model Voyager-DE ^™ STR spectrometer with dithranol as the matrix. The electronic spectrum was measured in a quartz cell with an optical path length of 1 cm using a JASCO model V-560 UV / VIS spectrometer with a temperature control mechanism. The infrared absorption spectrum was measured at 25 ° C. using a JASCO model FT / IR-660 _Plus Fourier transform infrared spectrometer. The X-ray diffraction pattern was measured at room temperature using a Rigaku model RINT-2500 diffractometer with CuKα as the radiation source. Scanning electron micrographs (SEM) were taken at 5 KV using a JEOL model JSM-6700F FE-SEM. Transmission electron micrographs were measured using a Philips model Tecnai F20 electron microscope with a Gatan slow scan CCD camera under low dose conditions. Methano [60] fullerenecarboxylic acid (Compound 8) was synthesized by the method of YP. Sun et al.

Synthesis of Compound 9 (Compound represented by Formula (4)):

Synthetic route

(1) Synthesis of Compound 1 Triethylene glycol (20.00 g, 133.18 mmol) was dissolved in tetrahydrofuran (THF, 50 ml), sodium hydroxide (10 ml, 2.66 M aqueous solution) was added at 0 ° C., and the mixture was stirred for 30 minutes. did. To this solution, p-toluenesulfonyl chloride (5.07 g, 26.62 mmol) dissolved in 20 ml of THF was added dropwise, stirred for 1 hour, warmed to room temperature, and further stirred for 9 hours. The reaction mixture was poured into ice water and extracted with dichloromethane (CH ₂ Cl ₂ ). The organic layer was washed with water, then hydrochloric acid (0.5N), and further with water, and then dried over anhydrous sodium sulfate. After the solvent was distilled off, the resulting residue was purified by silica gel chromatography (CH ₂ Cl ₂ / methanol (MeOH)) to obtain Compound 1 as a colorless oil (6.67 g, yield 82.24%).

(2) Synthesis of Compound 2 Compound 1 (6.00 g, 19.71 mmol) and 4-bromo-4′-hydroxybiphenyl (4.46 g, 17.92 mmol) were dissolved in dry THF (100 ml) under an argon atmosphere. , Potassium hydroxide (2.01 g, 35.84 mmol) was added, followed by heating for 19 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with CH ₂ Cl _{2. The} organic layer was washed with water, then hydrochloric acid (0.5 N), and further with water, and then dried over anhydrous sodium sulfate. After distilling off the solvent, the resulting residue was purified by silica gel chromatography (CH ₂ Cl ₂ / acetone) to obtain Compound 2 as a white solid (4.80 g, yield 70%).
¹ H-NMR (500 MHz, CDCl ₃ ) δ:
7.504 (d, J = 8.5Hz, 2H), 7.453 (d, J = 8.5 Hz, 2H),
7.386 (d, J = 8.5 Hz, 2H), 6.970 (d, J = 8.5 Hz, 2H),
4.161 (t, J = 5.0 Hz, 2H), 3.872 (t, J = 5.0 Hz, 2H),
3.700 (m, 6H), 3.611 (t, J = 4.0 Hz, 2H)

(3) Synthesis of Compound 3 Under an argon atmosphere, Compound 2 was dissolved in dry CH ₂ Cl ₂ (35 ml) and cooled to 0 ° C. Pyridine (1.16 ml, 15.74 mmol) was added to this solution, acetic anhydride (1.49 ml, 15.74 mmol) was added, and the mixture was stirred for 1 hour, warmed to room temperature, and further stirred overnight. The reaction mixture was washed twice with a saturated aqueous ammonium chloride solution and then with water, and then dried over anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel chromatography (CH ₂ Cl ₂ / acetone) to obtain Compound 3 as a white solid (3.37 g, yield 76%).
¹ H-NMR (500 MHz, CDCl ₃ ) δ:
7.506 (d, J = 9.0Hz, 2H), 7.452 (d, J = 9.0Hz, 2H),
7.387 (d, J = 9.0Hz, 2H), 6.963 (d, J = 9.0Hz, 2H),
4.211 (t, J = 5.0Hz, 2H), 4.156 (t, J = 5.0Hz, 2H),
3.865 (t, J = 5.0Hz, 2H), 3.696 (m, 6H), 2.052 (s, 3H)

(4) Synthesis of Compound 4 Under an argon atmosphere, Compound 3 (3.24 g, 7.64 mmol), bis-triphenylphosphopalladium dichloride (0.27 g, 0.38 mmol), copper iodide (0.14 g, 0 .76 mmol) was dissolved in 1,8-diazobicyclo [5,4,0] -7-undecene (DBU) (35 ml) and benzene (25 ml), and 4 '-{2- dissolved in benzene (25 ml) [2- (2-Methoxyethoxy) ethoxy] ethoxy} -4-biphenylylethyne (2.06 g, 7.64 mmol) was added dropwise, and the mixture was heated and stirred at 60 ° C. overnight. After cooling to room temperature, the reaction mixture was extracted by adding CH ₂ Cl ₂ , washed with a saturated aqueous ammonium chloride solution, and the organic layer was dried over sodium sulfate. Sodium sulfate was removed by decantation, and white solid compound 4 was collected by filtration from the CH ₂ Cl ₂ suspension (3.13 g, yield 60%).
¹ H-NMR (500 MHz, CDCl ₃ ) δ:
7.567 (d, J = 8.0Hz, 4H), 7.526 (m, 8H), 6.982 (d, J = 8.0Hz, 4H),
4.219 (t, J = 4.5Hz, 2H), 4.168 (t, J = 4.5Hz, 4H),
3.873 (t, J = 5.0Hz, 4H), 3.690 (m, 13H), 3.539 (t, J = 5.0Hz, 2H),
3.366 (s, 3H), 2.057 (s, 3H);
MALDI-TOF-MS: m / z:
As C ₄₁ H ₄₆ O ₉ , calculated: [M] ⁺ 682.3;
Actual value: 682.4.

(5) Synthesis of Compound 5 Compound 4 (1.00 g, 1.46 mmol) and 2,5-diphenyl-3,4-bis (4-n-dodecylphenyl) cyclopentadienone (1.06 g) under an argon atmosphere. , 1.46 mmol) was dissolved in diphenyl ether (4 ml) and stirred at 350 ° C. for 2 days. The reaction mixture was cooled to room temperature and purified by silica gel chromatography (CH ₂ Cl ₂ / acetone) and further by medium pressure liquid chromatography (CH ₂ Cl ₂ / acetone) to obtain Compound 5 as a white solid (1.47 g, Yield 73%).
¹ H-NMR (500 MHz, CDCl ₃ ) δ:
7.320 (d, J = 8.0Hz, 4H), 7.047 (d, J = 8.0Hz, 4H), 6.830 (m, 18H),
6.662 (d, J = 8.0Hz, 4H), 6.610 (d, J = 8.0Hz, 4H),
4.195 (t, J = 4.5Hz, 2H), 4.090 (t, J = 4.5Hz, 4H), 3.819 (m, 4H),
3.678 (m, 12H), 3.515 (m, 2H), 3.342 (s, 3H), 2.321 (t, J = 4.5 Hz, 4H),
2.037 (s, 3H), 1.369 (m, 4H), 1.236 (s, 32H), 1.073 (b, 4H),
0.859 (t, J = 7.0Hz, 6H),
MALDI-TOF-MS: m / z:
Calculated as C ₉₃ H ₁₁₅ O ₉ : [M + H] ⁺ 1375.8;
Actual value: 1375.5.

(6) Synthesis of Compound 6 Compound 5 (300 mg, 0.22 mmol) dissolved in methanol (20 ml) and THF (10 ml), and potassium hydroxide (002 g, 0.33 mmol) dissolved in water (1 ml) And stirred at room temperature for 1 hour. After the solvent was distilled off, CH ₂ Cl ₂ was added to the residue and washed with water. The organic layer was then dried over anhydrous sodium sulfate and the solvent was distilled off to obtain Compound 6 as a white solid (0.27 g, Yield 93%).
¹ H-NMR (500 MHz, CDCl ₃ ) δ:
7.320 (m, 4H), 7.046 (d, J = 9.0 Hz, 4H), 6.827 (m, 18H),
6.663 (d, J = 8.0 Hz, 4H), 6.611 (d, J = 8.0 Hz, 4H), 4.194 (m, 4H),
3.821 (m, 4H), 3.647 (m, 14H), 3.513 (t, J = 5.0 Hz, 2H), 3.342 (s, 3H),
2.322 (t, J = 8.0 Hz, 4H), 1.370 (m, 4H), 1.236 (m, 32H), 1.071 (b, 4H),
0.860 (t, J = 7.0 Hz, 6H);
MALDI-TOF-MS: m / z:
As C ₉₁ H ₁₁₃ O ₈ , calculated: [M + H] ⁺ 1333.8;
Actual value: 1333.8.

(7) Synthesis of Compound 7 (HBC-TNF) Compound 6 (300 mg, 0.22 mmol) was dissolved in dry CH ₂ Cl ₂ (100 ml), dry argon was bubbled into the solution for 10 minutes, and then MeNO ₂ (4 ml). Iron (III) chloride dissolved in was gradually added and further stirred at 25 ° C. for 1 hour. The reaction mixture was poured into methanol (200 ml) with stirring, and the precipitated solid was collected by filtration and purified by silica gel column chromatography (SiO ₂ / hot THF). Further, recrystallization from THF gave Compound 7 as a yellow viscous solid (140 mg, 62% yield).
¹ H-NMR (500 MHz, THF-d ₈ , 55 ° C.) δ:
8.47 (s, 2H), 8.38 (s, 2H), 8.23-8.07 (br, 8H), 7.73 (br, 4H),
7.37 (br, 2H), 7.14 (br, 4H), 4.30 (br, 4H), 3.98 (br, 4H),
3.79-3.61 (m, 16H), 3.35 (s, 3H), 2.88 (br, 4H), 1.89 (br, 4H),
1.58-1.28 (br, 36H), 0.85 (br, 6H);
MALDI-TOF-MS: m / z:
As C ₉₁ H ₁₀₀ O ₈ , calculated: [M] ⁺ 1320.74;
Actual value: 1320.89.

(8) Synthesis of Compound 9 Compound 7 (107 mg, 0.081 mmol), dicyclohexylcarbodiimide (DCC) (62 mg, 0.30 mmol) and dimethylaminopyridine (DMAP) (37 mg, 0.30 mmol) were added at room temperature under an argon atmosphere. A suspension formed by dissolving in a dry CH ₂ Cl ₂ -Bromobenzene mixed solvent (8 ml) (V / V, 3/1) and adding methano [60] fullerenecarboxylic acid (compound 8) (94 mg, 0.12 mmol). The liquid was reacted under reflux for 24 hours. The reaction solution was filtered to remove the precipitate, and then the filtrate was washed with hydrochloric acid (0.1N), a saturated aqueous NaHCO ₃ solution, and Brain. The organic layer was separated and dried over MgSO ₄ , and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (CHCl ₃ / CH ₃ OH, 100/1, v / v), and further purified by reprecipitation from CHCl ₃ / THF three times to give compound 9 as a brown solid (100 mg Yield 59%).
MALDI-TOF-MS: m / z:
As C ₁₅₃ H ₁₀₀ O ₉ , calculated: [M] ⁺ 2080.74;
Actual measurement value: 2080.88.
Absorption based on hexaperihexabenzocoronene (HBC) was observed at 365 and 395 nm in the UV-visible absorption spectrum measurement (FIG. 2).

Synthesis of Compound 13 (Compound represented by Formula (5)):

Synthetic route

(1) Synthesis of compound 2 (4-bromo-4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} biphenyl)
4- (4′-bromophenyl) phenol (3.00 g, 0.012 mol) and 1- (4-toluenesulfonyl) triethylene glycol monomethyl ether (Compound 1) (4.2 g, 0.0132 mol, 1.1 equivalents) ) Was dissolved in a minimum amount of anhydrous N, N-dimethylformamide (˜30 ml) and anhydrous potassium carbonate (4 g, 3.3 eq) was added. The resulting suspension was heated and reacted for 24 hours with stirring, and the reaction solution was cooled to room temperature, and then poured into water (100 ml) and the produced white precipitate was filtered. The white precipitate separated by filtration was dissolved in dichloromethane (100 ml) and dried over Na ₂ SO ₄ overnight. After filtering off Na ₂ SO ₄ , dichloromethane in the filtrate was distilled off to give 4-bromo-4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} biphenyl (compound 2) as a white powder. (4.3 g, 0.0109 mol, yield 91%). The obtained white powder was subjected to the next reaction as it was.
Analytical value: ¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.50 (d, J = 8.55 Hz, 2H), 7.45 (d, J = 8.55 Hz, 2H),
7.39 (d, J = 8.55 Hz, 2H), 6.96 (d, J = 8.55 Hz, 2H),
4.15 (t, J = 4.88 Hz, 2H), 3.86 (t, J = 4.88 Hz, 2H),
3.74 (m, 2H), 3.67 (m, 2H), 3.65 (m, 2H) 3.53 (m, 2H), 3.36 (s, 3H).

(2) Synthesis of Compound 10 (1,2-bis- (4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} -4-biphenylylethyne) 4-bromo-4 ′-{2 -[2- (2-methoxyethoxy) -ethoxy] -ethoxy} -biphenyl (compound 2) (4 g, 0.01 mol), DBU (9.2 g, 6 eq), PdCl ₂ (PPh ₃ ) ₂ (425 mg, 6 %) And CuI (192 mg, 10%) dissolved in benzene (20 ml) at room temperature with stirring and warmed to 60 ° C. to trimethylsilylethine (TMSE) (0.71 ml, 0, 496 g, 0.5 eq) Water (70 μL, 0.4 eq) was immediately added, and after 24 hours of reaction at 60 ° C., the product was filtered off and washed with a small amount of ice-cold dichloromethane. Purify by column chromatography eluting with dichloromethane / methanol (gradient gradient 1-5% methanol) or recrystallize from toluene solution to give 1,2-bis- (4 '-{2- [2- (2-Methoxyethoxy) ethoxy] ethoxy} -4-biphenylylethyne (Compound 10) was obtained (2.3 g, yield 71%).
Analytical value: ¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.57-7.51 (m, 6H), 6.97 (d, J = 9.15 Hz, 4H),
4.15 (t, J = 4.88 Hz, 4H), 3.86 (t, J = 4.89 Hz, 4H),
3.74 (m, 4H), 3.68, (m, 4H), 3.64 (m, 4H), 3.54 (m, 4H),
3.36 (s, 6H).
MALDI-TOF (dithranol): m / z = 655.31 (M + H) ⁺ .

(3) Synthesis of Compound 11 (2,5-diphenyl-3,4-bis (4-n-dodecylphenyl) cyclopentadienone) 1,2-bis- (4-n-dodecylphenyl) -1,2 -Dissolve diketone (1.5 g, 2.75 x 10 ^-3 mol) and dibenzyl ketone (0.58 g, 2.76 x 10 ^-3 mol) in dioxane and heat to 100 ° C to obtain tetrabutylammonium hydroxy 1.0M solution in methanol (1 eq, 2.76 ml) was added in one portion and heated for an additional 15 minutes. The reaction mixture was poured into water and extracted with dichloromethane, and the extract was evaporated to dryness and purified by column chromatography using silica gel eluting with dichloromethane / hexane (gradient gradient 10-50% dichloromethane). Further purification by preparative HPLC, eluting with dichloromethane / n-hexane (1: 3), evaporated to dryness and 2,5-diphenyl-3,4-bis (4-n-dodecylphenyl) cyclopentadienone ( Compound 11) was obtained as a purple powder (0.88 g, 44% yield).
Analytical value: ¹ H-NMR (500 MHz, CDCl ₃ ): δ
~ 7.24 (m), 6.96 (d, J = 7.94 Hz, 4H), 6.80 (d, J = 7.94 Hz, 4H),
2.55 (t, J = 7.63 Hz, 4H), 1.56 (br., 4H), 1.26 (br., 36H),
0.88 (t, J = 6.71 Hz, 6H).
MALDI-TOF (dithranol): m / z = 720 (M ⁺ ).

(4) Compound 12 (1,4-diphenyl-2,3-bis (4-n-dodecylphenyl) -5,6-bis (4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy } -4-biphenylyl) benzene) 2,5-diphenyl-3,4-bis (4-n-dodecylphenyl) cyclopentadienone (Compound 11) (0.6 g, 8.3 × 10 ⁻⁴ mol) ) And 1,2-bis- (4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} -4-biphenylylethyne (Compound 12) (0.52 g, 7.9 × 10 ⁻⁴ mol) was suspended in Schlenk in diphenyl ether (1.5 ml), refluxed (~ 300 ° C) for 24 hours, and then cooled to room temperature.The reaction mixture was dissolved in acetone and unreacted through a silica column. 1, 2 Bis- (4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} -4-biphenylylethyne was removed, and then the solvent was distilled off from the solution, followed by chromatography on silica gel (eluent: Dichloromethane / hexane, concentration gradient dichloromethane / hexane (3/2) to dichloromethane (100%)) to obtain a light brown powder (0.75 g, yield 70%).
Analytical value: 1H-NMR (500 MHz, CDCl ₃ ): δ
7.32 (d, J = 9.16 Hz, 4H), 7.05 (d, J = 8.55 Hz, 4H),
6.82 (m, 18H) 6.67 (d, J = 7.94 Hz, 4H), 6.61 (d, J = 8.55 Hz, 4H),
4.09 (t, J = 4.88 Hz, 4H), 3.82, (t, J = 4.88 Hz, 4H),
3.71 (m, 4H), 3.64 (m, 8H) 3.52 (m, 4H), 3.34 (s, 6H),
2.33 (t, J = 7.63 Hz, 4H), 1.37 (m, 4H) 1.24 (m, 34H),
1.08 (br., 4H), 0.86 (t, J = 6.71 Hz, 6H).
MALDI-TOF (dithranol): m / z = 1348.27 (M ⁺ ).

(5) Compound 13 (2,5-di-n-dodecyl-11,14-bis (4- {2- [2- (2-methoxyethoxy) ethoxy] ethoxy} phenyl) -hexa-peri-hexabenzocoronene) Synthesis of 1,4-diphenyl-2,3-bis (4-n-dodecylphenyl) -5,6-bis (4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} -4- Biphenylyl) benzene (0.70 g, 5 × 10 ⁻⁴ mol) was dissolved in dry dichloromethane (200 ml) and stirred at room temperature while blowing argon gas through a glass tube. When anhydrous FeCl ₃ (2.7 g, 0.017 mol, 34 eq) was dissolved in nitromethane (5 ml) and added little by little to the above solution, the color of the solution changed from dark red to black to orange. Stirring was continued for another 90 minutes, after which methanol (100 ml) was added to quench. The yellow precipitate formed was filtered off and purified first by column chromatography (silica gel, CH ₂ Cl ₂ / methanol = 300: 10) and then purified by GPC (Bio-Rad BioBeads X-1, dichloromethane eluent). did. Further purification with dichloromethane / methanol gave a yellow gel which was dried in vacuo and 2,5-di-n-dodecyl-11,14-bis (4- {2- [2- (2-methoxy Ethoxy) ethoxy] ethoxy} phenyl) -hexa-peri-hexabenzocoronene was obtained as a tan solid (0.49 g, 73% yield).
Analytical value: ¹ H-NMR (500 MHz, CDCl ₃ ): δ
8.05 (s, 2H), 7.95 (s, 2H), 7.79 (d, J = 8.54 Hz, 2H),
7.71 (d, J = 7.94 Hz, 2H) 7.59 (s, 2H), 7.56 (s, 2H),
7.52 (d, J = 7.93 Hz, 4H), 7.10 (d, J = 7.93 Hz, 4H),
7.07 (m, 2H), 4.32 (br. 2H), 4.06 (t, J = 4.56 Hz, 4H),
3.92 (m, 4H), 3.85 (m, 4H), 3.79 (m, 4H), 3.67 (m, 4H),
3.47 (s, 6H), 2.59 (br. T, 4H), 1.69 (br., 4H),
1.46-1.30 (m, 36H), 0.89 (t, J = 7.02 Hz, 6H).
MALDI-TOF (dithranol): m / z = 1335.75 (M ⁺ )

Simultaneous self-assembly The molar ratio of the compound 9 obtained in Example 1 and the compound 13 obtained in Example 2 is 0: 100, 10:90, 25:75, 40:60, 50:50, 60:40, 75: A toluene solution obtained by mixing at 25, 90:10, 100: 0 and heating and dissolving (both 0.2 mM in total for both molecules) was allowed to cool to room temperature and allowed to stand for 1 day. A turbid liquid was obtained.

Electron microscope observation Precipitates were collected from each suspension obtained in Example 3, and a scanning electron microscope (SEM) image and a transmission electron microscope (TEM) image were observed. The results are shown in FIGS. 3 and 4 (mixing ratio of compound 9 and compound 13 (a) 0: 100, (b) 25:75, (c) 50:50, (d) 75:25, (e) 100. : 0). It was confirmed that the nanotube structure was quantitatively generated at any mixing ratio (FIGS. 3 and 4).
Moreover, when the diameter of the nanotube observed from the transmission electron microscope was plotted, it was confirmed that the diameter increased from 20 nanometers to 22 nanometers as the mixing ratio of Compound 9 increased (FIG. 5).
Furthermore, when the structure of the wall of the nanotube is examined in detail, when the molar fraction of compound 13 is 100%, the wall is observed with a single black line, whereas the proportion of compound 9 increases. It changed into two lines, and it was confirmed that the inner and outer surfaces of the wall were systematically covered with fullerene (FIG. 6). These strongly suggest that both molecules are mixed in each nanotube, rather than each molecule forming a nanotube separately due to simultaneous self-assembly.

Fluorescence Quenching Precipitates were collected from each suspension obtained in Example 3, and fluorescence was measured to obtain the results shown in FIG. Fluorescence observed in the vicinity of 520 nanometers when irradiated with light having an excitation wavelength of 355 nanometers in the nanotube made of compound 13 is 90% or more quenched by adding 10 mol% of compound 9, and almost 25% or more. Quenched completely. This indicates that electrons excited by light irradiation and generated at the HBC site have moved to the fullerene site.

Transient light absorption spectrum Using a thin film prepared by dropping a suspension consisting only of compound 13 obtained in Example 3 and a suspension containing 10% of compound 9 onto a substrate, a transient light absorption spectrum was obtained. Measurements were made and the results shown in FIGS. 8 and 9 were obtained. In the transient light absorption spectrum after irradiation with excitation light having a wavelength of 355 nanometers using a thin film of nanotubes consisting only of compound 13, only strong bleaching is observed at 460 nanometers, but compound 9 is 10 mol%. In the transient light absorption spectrum of the added nanotube, a peak derived from the HBC radical cation was observed around 605 nanometers (FIG. 8). This strongly suggests that electron transfer from HBC to fullerene occurs after photoexcitation.
The time-resolved profile of the peak observed at 605 nanometers in the transient light absorption spectrum of the nanotube thin film to which 10% of compound 9 was added showed very good agreement with the time-resolved profile of microwave conductivity using the same sample. (FIG. 9). This strongly indicates that the generation / annihilation of the charge separation state by photoinduced electron transfer coincides with the generation / annihilation of photocarriers.

Measurement of photoconductivity characteristics by stationary light A nanotube thin film was fabricated on a silicon substrate having a silicon oxide film (200 nanometers), a gold electrode was vacuum-deposited on it, and the photoconductivity was measured by irradiation of steady light. . FIG. 11 (a) shows the current-voltage characteristics when the nanotube 9 comprising the compound 9 is irradiated with stationary light (xenon lamp, wavelength 300-650 nanometers) and when it is not irradiated, and FIG. FIG. 11C shows the current-voltage characteristics when the molar fraction of the compound 9 in the nanotube is changed. The current-voltage characteristics under light irradiation showed an ohmic behavior, and a photocurrent was observed almost in proportion to the amount of light. This indicates that optical carriers are generated according to the light intensity. It was also clarified that photocurrent can be switched sharply and reproducibly by turning light on and off.

Correlation between Steady Photoconductivity and Microwave Conduction Generally, photocurrent is proportional to the product of carrier mobility (μ), lifetime (/ _{1 / e} ), and light-carrier conversion efficiency (φ). Therefore, when φΣμmax X τ / _{1 / e} obtained by the microwave conductivity is plotted against the molar fraction of the nanotube, this behavior and certain conditions in the steady state photoconductivity measurement (external voltage +10 V, light density 0 It was confirmed that the behaviors of the plots of the photocurrent values at .91 mW / mm ² ) matched very well (FIG. 12).

  As described above, the present invention provides a photoconductive material comprising a nano-sized structure formed by simultaneous self-assembly, preferably a supramolecular nanotube, and the photoconductive material of the present invention comprises: The present invention provides a novel electronic material, and is applied to many electronic component materials as a light detection element, a light switching element, a photoresponsive charge transport element, and the like. The electronic component material of the present invention can be applied to, for example, a solar cell material, a light detection element material, a nanodevice such as a molecular lead, and the like.

FIG. 1 schematically shows a layer structure of a nanotube in which a compound represented by the general formula (1) and a compound represented by the general formula (2) of the present invention are simultaneously self-assembled. FIG. 2 is a chart of an ultraviolet-visible absorption spectrum of the compound 9 (HBC-C ₆₀ ) of the present invention in a chloroform solution. FIG. 3 is a photograph, instead of a drawing, showing an SEM image of a nanotube produced by simultaneously self-assembling compound 9 and compound 13 of the present invention at each mixing ratio (compound 9: compound 13). FIG. 4 is a photograph, instead of a drawing, showing a TEM image of a nanotube produced by simultaneously self-assembling compound 9 and compound 13 of the present invention at each mixing ratio (compound 9: compound 13). FIG. 5 is a chart showing the diameters of nanotubes produced by simultaneous self-assembly of Compound 9 and Compound 13 of the present invention at each mixing ratio (Compound 9: Compound 13). FIG. 6 is a photograph replacing a drawing, showing the wall thickness (TEM image) of a nanotube produced by simultaneously self-assembling compound 9 and compound 13 of the present invention at each mixing ratio (compound 9: compound 13). . FIG. 7 shows a chart of the fluorescence spectrum of a nanotube comprising the compounds 9 and 13 of the present invention (FIG. 7 (a)). In FIG. 7A, the molar fraction of compound 9 is 0% (red in the original drawing), 10% (blue in the original drawing), and 100% (green in the original drawing). FIG. 7B is a graph plotting the fluorescence intensity against the molar fraction of Compound 9. FIG. 8 shows a chart of the transient light absorption spectrum of the nanotube made of the compound 13 (FIG. 8 (a)). FIG. 8 (b) shows a chart of transient light absorption spectra of a nanotube composed of 10 mol% of Compound 9 and 90 mol% of Compound 13. FIG. 9 shows the time-resolved profile of the transient light absorption spectrum intensity (red in the original figure) and microwave conductivity (blue in the original figure) at a wavelength of 605 nanometers in a nanotube composed of 10 mol% of compound 9 and 90 mol% of compound 13. ) Chart. FIG. 10 shows a chart of the time-resolved microwave conductivity profile of nanotubes composed of compound 9 and compound 13 (FIG. 10 (a)). In FIG. 10 (a), the molar fraction of compound 9 is 0% (red in the original drawing), 10% (blue in the original drawing), 25% (orange in the original drawing), 40% (yellow in the original drawing), 50% ( Pink in the original map), 75% (purple in the original map), 100% (green in the original map). FIG. 10B is a graph plotting the maximum value of photoconductivity. 11, when the nanotubes of light non-irradiated consisting of compounds 9 (purple in originals) and the light irradiation time of the current - voltage characteristics (optical density 0.076mW / mm ² (blue in originals), 0.35 mW / ^mm 2 ( (Red in the original map), 0.91 mW / mm ² (green in the original map)) is shown (FIG. 11 (a)). FIG. 11B shows a chart of current switching characteristics by light irradiation / non-irradiation at a light density of 0.91 mW / mm ² . FIG. 11 (c) is a graph showing current-voltage characteristics during light irradiation of a nanotube containing compound 9 in various molar fractions at a light density of 0.91 mW / mm ² . Represents the mole fraction. FIG. 12 is a graph in which the lifetime of the optical carrier obtained from the time-resolved microwave conductivity profile is plotted (FIG. 12 (a)). FIG. 12 (b) shows a plot of photocurrent value (green in the original figure) under time-resolved microwave conductivity measurement and a plot of photocurrent value under 0.91 mW / mm ² light irradiation when a 10 V voltage is applied. It is a plot of the product of the maximum value and the lifetime of the optical carrier (red in the original figure).

Claims (10)

The following general formula (1),
[Wherein, R ¹ represents an alkyl group having 10 to 30 carbon atoms, R ² and R ³ represent C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) nOR ⁴ (where R ⁴ represents a hydrogen atom, an alkyl group) Group or formula (3)
Represents a methano [60] fullerenecarboxylic acid group which may include a metal represented by the formula: R ² and R ³ may be the same or different from each other, but at least one of R ² and R ³ is a metal And methano [60] fullerenecarboxylic acid group which may encapsulate n, and n represents a positive integer. ). ]
A hexaperihexabenzocoronene derivative having in its molecule a group having fullerene which may contain a metal represented by the following general formula (2),
[Wherein, R ⁵ represents an alkyl group having 10 to 30 carbon atoms, and R ⁶ represents C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) nOR ⁷ (where R ⁷ represents a hydrogen atom or an alkyl group. , N represents a positive integer.]
A self-assembled nano-sized structure comprising a hexaperihexabenzocoronene derivative that does not have a fullerene-containing group that may contain a metal represented by   The self-assembled nano-sized structure according to claim 1, wherein the self-assembled nano-sized structure is a nanotube formed by self-assembly. Hexperihexabenzocoronene derivative having in its molecule a group having fullerene which may contain metal and hexaperihexabenzobenzocorene having no group having fullerene which may contain metal in its molecule to the number of moles of the total derivative, according to claim 1 or 2 mole fraction of hexamethylene Peri hexabenzocoronene derivative is 5% to 90% having a group having a good fullerenes also be contained metal in the molecule Self-assembled nano-sized structure. The self-assembled nano-sized structure according to any one of claims 1 to 3 , wherein a mole fraction of a hexaperihexabenzocoronene derivative having a group having a fullerene which may include a metal in a molecule is 5 to 50%. The hexaperihexabenzocoronene derivative represented by the general formula (1) is represented by the following formula (4)
The self-assembled nano-sized structure according to claim 1 , wherein The hexaperihexabenzocoronene derivative represented by the general formula (2) has the following formula (5)
The self-assembled nanosized structure according to any one of claims 1 to 5 , wherein Light detecting elements consisting of self-assembled nano-sized structure according to any one of claims 1-6. The optical switching element which consists of a self-organization nanosize structure in any one of Claims 1-6 . Photoresponsive charge transporting device consisting of self-assembled nano-sized structure according to any one of claims 1-6. The electronic component material containing at least 1 sort (s) of the element in any one of Claims 7-9 .