JP5004151B2 - Novel hexabenzocoronene derivative and photoconductive nanotube comprising the same - Google Patents

Description

  The present invention relates to a novel hexabenzocoronene derivative having an electron-accepting group in the molecule, more specifically a novel hexabenzocoronene derivative represented by the general formula (1), and a nanostructure formed by self-assembly thereof. The present invention relates to a structure having a size, a photoconductive nanotube made of the structure, and a photodetecting element, a photoswitching element, and a photoresponsive charge transporting element including the nanosized structure.

In recent years, research and development on electronic devices using organic molecules and polymer compounds have been actively conducted. Advantages of using an organic substance as an electronic device include a lighter element, a flexible structure, and a simplified process. Further, as each element is miniaturized, a bottom-up element structure manufacturing process using molecules as a minimum unit has attracted attention. However, devices that can operate with one molecule as one element have been in the research stage, but have not yet been put into practical use. The reason for this is that the size of a single molecule is several nanometers or less, and it is too small to be incorporated using the current microfabrication technology for semiconductor device fabrication. Therefore, it can be considered that organic molecular devices represented by liquid crystals, organic EL elements and the like that are currently in practical use utilize the properties of organic molecules as bulk.
On the other hand, each supramolecular nanotube is a structure having a diameter of about 20 nm, and can be used as a functional nanomaterial having each nanotube as a structural unit. Is different.

As an approach to constructing functional nanomaterials that support such supramolecular nanotechnology, a bottom-up method based on a self-assembly process has attracted attention. This is a technique of utilizing spontaneous and hierarchical integration of small molecules having associative properties in a solution, for example. It is known that structures such as vesicles, fibers, ribbons, and tubes can be obtained by this method. However, what has been conventionally used as a molecule constituting these nanostructures are amphiphilic compounds such as lipids, which have poor electronic and photochemical properties, etc. It does not indicate the property to be.
In contrast, the present inventors focused on hexaperihexabenzocoronene (HBC) as a basic element for constructing nanostructures, and introduced a hydrophilic substituent and a hydrophobic substituent into the HBC skeleton to reduce the diameter to about It has been reported that supramolecular nanotubes having a 20 nm aspect ratio of 5000 or more can be easily and quantitatively obtained by a solution process (see Patent Documents 1 and 2). In this HBC nanotube, the HBC plane is helically arranged by π-stacking interaction, and charge carriers (holes) are easily formed by chemical doping to exhibit conductivity (resistivity: 10 Ωcm). As the donor-acceptor system containing such hexaperihexabenzocoronene, the systems described in the following non-patent documents 1 to 3 are known, and these are all perylene and TNF in the hexaperihexabenzocoronene molecule. It is a system doped with electron-accepting molecules such as.
In addition, the use of hexabenzocoronenes as organic semiconductor materials has been reported (see Patent Documents 3 to 6), and the development of solar cells using such organic semiconductors has also been reported (see Patent Document 7). ). Further, paying attention to the properties of hexabenzocoronene as a charge transport material, it has been reported that a hexabenzocoronene derivative having a tertiary amine is used as an acid scavenger on the surface of the photosensitive layer of an electrophotographic photoreceptor. . This is because the surface of the photosensitive layer of the electrophotographic photosensitive member is subjected to acid scavenging to neutralize such oxidizing substances in the photosensitive layer in order to prevent repeated use and deterioration due to oxidizing substances caused by the surrounding environment. As a chemical agent, a hexabenzocoronene derivative having a tertiary amine, which is a basic and charge transporting substance, has been developed (see Patent Document 8).

Japanese Patent Laid-Open No. 2005-220046 JP-A-2005-220047 JP 2004-158709 A JP 2005-79163 A JP 2006-41495 A JP 2005-504663 A JP 2003-168492 A JP 2005-48336 A L. Schmidt-Mende, et al., Science, 293, 1119 (2001) C. Im, W. Tian, et al., Syn. Metals, 139, 683 (2003) C. Im, W. Tian, et al., J. Chem. Phys., 119, 3952 (2003)

  The present invention provides a novel hexaperihexabenzocoronene derivative useful as a supermolecular nanotube material having photoconductive properties, a supermolecular nanotube having photoconductive properties using the same, and the like.

As a donor-acceptor system containing hexaperihexabenzocoronene, all hexaperihexabenzocoronene molecules are doped with electron-accepting molecules such as perylene and 4,5,7-trinitro-9-fluorenone (TNF). The present inventors have developed nano-sized nano-size films formed by self-assembly of hexaperihexabenzocoronene derivatives having an electron-donating hexaperihexabenzocoronene moiety and an electron-accepting moiety in the same molecule without doping. We have been studying the development of structural molecules. For this purpose, the present inventors have designed HBC derivative molecules having various substituents precisely, and have intensively studied the influence of the type of hydrophilic substituents on the association behavior and the conductivity of the obtained HBC nanotubes. As a result, by introducing 4,5,7-trinitro-9-fluorenone (TNF) having a strong electron accepting property at the tip of the hydrophilic substituent, the conductivity is greatly changed by light irradiation, that is, photoconductivity. The inventors have found that HBC nanotubes having the above can be obtained, and have reached the present invention.
That is, the present invention provides the following general formula (1)

[Wherein, R ¹ independently represents an alkyl group, and R ² and R ³ each independently represent the following general formula (2)
—C ₆ H ₄ —O—R ⁵ — (O—R ⁶ ) _n —OR ⁴ (2)
(In the formula, —C ₆ H ₄ — represents a phenylene group, R ⁴ represents a hydrogen atom, an alkyl group or an electron-accepting group, and R ² and R ³ may be the same as or different from each other. R ⁴ group of at least one of ² and R ³ is an electron accepting group, R ⁵ and R ⁶ each independently represents an alkylene group, and n represents a positive integer.)
X represents a hydrogen atom or an organic group. ]
It is related with the hexaperihexabenzocoronene derivative represented by these.
The present invention also relates to a nano-sized structure formed by self-assembly of a hexaperihexabenzocoronene derivative represented by the general formula (1).
Furthermore, the present invention relates to a light detection element and a light switching element comprising a nano-sized structure formed by self-organization of the hexaperihexabenzocoronene derivative represented by the general formula (1).
The present invention also relates to a photoresponsive charge transport device comprising a nano-sized structure formed by self-assembly of the hexaperihexabenzocoronene derivative represented by the general formula (1).
Furthermore, the present invention relates to an electronic component material containing at least one of the above-described photodetecting element, photoswitching element, or photoresponsive charge transport element of the present invention.
The present invention will be described in more detail as follows.
(1) The following general formula (1)

[Wherein, R ¹ independently represents an alkyl group, and R ² and R ³ each independently represent the following general formula (2)
—C ₆ H ₄ —O—R ⁵ — (O—R ⁶ ) _n —OR ⁴ (2)
(In the formula, —C ₆ H ₄ — represents a phenylene group, R ⁴ represents a hydrogen atom, an alkyl group or an electron-accepting group, and R ² and R ³ may be the same as or different from each other. R ⁴ group of at least one of ² and R ³ is an electron accepting group, R ⁵ and R ⁶ each independently represents an alkylene group, and n represents a positive integer.)
X represents a hydrogen atom or an organic group. ]
A hexaperihexabenzocoronene derivative represented by:
(2) The hexaperihexabenzocoronene according to (1), wherein R ⁵ and R ⁶ in R ² and R ³ in the general formula (1) are each independently an ethylene group (—CH ₂ CH ₂ —). Derivative.
(3) The electron accepting group of the R ⁴ group in R ² and R ³ of the general formula (1) is a 4,5,7-trinitro-9-fluorenone (TNF) -2-carbonyl group (1 Or the hexaperihexabenzocoronene derivative according to (2).
(4) The organic group in X of the general formula (1) is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, The hexaperihexabenzocoronene derivative according to any one of (1) to (3), which is a group selected from the group consisting of a cyano group, an amide group, an acyl group, and a substituted silyl group.
(5) The hexaperihexabenzocoronene derivative according to any one of (1) to (4), wherein R ^{1 in the} general formula (1) is independently an alkyl group having 10 to 30 carbon atoms.
(6) At least one of R ² and R ³ in the general formula (1) is represented by the following formula: —C ₆ H ₄ —OCH ₂ CH ₂ — (OCH ₂ CH ₂ ) _n —OCO-TNF
(In the formula, —C ₆ H ₄ — represents a phenylene group, and TNF represents a 4,5,7-trinitro-9-fluorenone (TNF) yl group.)
The hexaperihexabenzocoronene derivative according to any one of (1) to (5), which is a group represented by the formula:
(7) The hexaperihexabenzocoronene derivative represented by the general formula (1) has the following formula (3)

The hexaperihexabenzocoronene derivative according to (6) above, which is a compound represented by the formula:
(8) A nano-sized structure formed by self-assembly of the hexaperihexabenzocoronene derivative according to any one of (1) to (7).
(9) The structure according to (8), wherein the nano-sized structure formed by self-assembly is a nanotube.
(10) The structure according to (8) or (9), wherein the structure is photoconductive.
(11) A photodetecting element comprising a nano-sized structure formed by self-assembly of the hexaperihexabenzocoronene derivative according to any one of (1) to (7).
(12) An optical switching element comprising a nano-sized structure formed by self-assembly of the hexaperihexabenzocoronene derivative according to any one of (1) to (7).
(13) A photoresponsive charge transport device comprising a nano-sized structure formed by self-assembly of the hexaperihexabenzocoronene derivative according to any one of (1) to (7).
(14) An electronic component material containing at least one element according to any one of (11) to (13).

  The compound represented by the general formula (1) of the present invention has HBC as an electron donor site and an electron accepting group as an electron acceptor site, for example, TNF in the same molecule. In addition, the supramolecular nanotube formed by self-assembly of the compound in a solution having both a hydrophilic portion and a hydrophobic portion includes an HBC skeleton that forms a π stack, and a nanotube. It is comprised by the electron-accepting group which covers the inner surface and outer surface of this. When this supramolecular nanotube is irradiated with light, the excited electrons are trapped in the TNF site as an electron acceptor, and charge carriers (holes) move smoothly in the HBC column, thereby exhibiting photoconductive characteristics. Thus, a material in which an independent supramolecular nanotube having a diameter of about 20 nanometers formed by self-assembly has a function such as photoconductivity is not yet known, and the present invention provides for the first time.

The compound represented by the general formula (1) of the present invention will be described in more detail.
The alkyl group in R ¹ of the general formula (1) of the present invention 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 (however, In the case of a cyclic group, the number of carbon atoms is 3 or more.), And preferred specific examples include, for example, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, A heptadecyl group, an octadecyl group, a nonadecyl group, etc. are mentioned, These groups 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. These alkyl groups may be substituted with a substituent that does not affect the physical properties.
R ² and R ³ in the general formula (1) of the present invention are groups represented by the general formula (2), and examples of the alkyl group in R ⁴ of the general formula (2) include 1 carbon atom. -20, preferably 1-10, more preferably 1-6 linear, branched or cyclic (however, in case of cyclic, the number of carbons is 3 or more) alkyl groups, specific examples As, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group Etc. These alkyl groups may be substituted with a substituent that does not affect the physical properties.
Further, the electron-accepting group in R ⁴ of the general formula (2) is not particularly limited as long as it is an organic group having an electron-accepting function. Preferred examples of the electron-accepting group include 4 , 5,7-trinitro-9-fluorenone (TNF), perylene diimide (PdI), tetracyanoquinodimethane (TCNQ), and the like, and the TNF group is directly bonded to the adjacent oxygen atom. However, a group that can be bonded to an adjacent oxygen atom through a functional group such as a carbonyl group is preferable. Preferred examples of the electron-accepting group include the following formulas:

The 4,5,7-trinitro-9-fluorenone (TNF) -2-carbonyl group represented by these is mentioned, However, It is not limited to this.
Examples of the alkylene group in R ⁵ and R ⁶ of the general formula (2) include a linear or branched divalent group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms. Specific examples thereof include ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group and the like. These alkylene groups may be substituted with a substituent that does not affect the physical properties.
The phenylene group in the general formula (2) may be a divalent phenylene group such as a p-phenylene group or an m-phenylene group, and a preferred phenylene group is a p-phenylene group. These phenylene groups may be substituted with a substituent that does not affect the physical properties.
N in the general formula (2) is a positive integer of 1 or more, preferably an integer of 2 or more, more preferably 2 to 20, 2 to 10, or 2 to 5.

Specific examples of the group represented by R ² and R ³ represented by the general formula (2) include, 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
_{-C 6 H 4 -OCH 2 CH 2} (OCH 2 CH 2) n -OCOTNF , and among them,
_{-P-C 6 H 4 -OCH 2} CH 2 (OCH 2 CH 2) 2 -OH,
_{-P-C 6 H 4 -OCH 2} CH 2 (OCH 2 CH 2) 3 -OH,
_{-P-C 6 H 4 -OCH 2} CH 2 (OCH 2 CH 2) 4 -OH,
_{-P-C 6 H 4 -OCH 2} CH 2 (OCH 2 CH 2) 2 -OCH 3,
_{-P-C 6 H 4 -OCH 2} CH 2 (OCH 2 CH 2) 3 -OCH 3,
_{-P-C 6 H 4 -OCH 2} CH 2 (OCH 2 CH 2) 4 -OCH 3,
_{-P-C 6 H 4 -OCH 2} CH 2 (OCH 2 CH 2) 3 -OCOTNF
[In the above formula, TNF represents a 4,5,7-trinitro-9-fluorenone (TNF) yl group. ]
Although the group etc. which are represented by are mentioned as a more preferable example, of course, it is not limited to these.

In the general formula (1) of the present invention, the organic group represented by X is a hindrance when the amphiphilic hexaperihexabenzocoronene derivative of the present invention is produced and used (for example, functional nanotube production). Any organic group may be used, for example, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group , A cyano group, an amide group, an acyl group, a substituted silyl group, and the like. Preferably, for example, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, cyano group, amide group, acyl group, and Examples thereof include an organic group consisting of a group selected from the group consisting of substituted silyl groups.
As the alkyl group, for example, a linear, branched or cyclic group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms (provided that the cyclic group has 3 or more carbon atoms) )), And more specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, Examples include a hexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the alkenyl group include those having one or more double bonds in the aforementioned alkyl group having 2 or more carbon atoms, and more specifically, vinyl group, allyl group, 1-propenyl group, isopropenyl. Group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like.
Examples of the alkynyl group include those having one or more triple bonds in the aforementioned alkyl group having 2 or more carbon atoms, and more specifically, an ethynyl group, a 1-propynyl group, a 2-propynyl group, and the like. Can be mentioned.
Examples of the aryl group include monocyclic, polycyclic or condensed cyclic aromatic hydrocarbon groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and more specifically. Examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.
Examples of the aralkyl group include monocyclic, polycyclic or condensed cyclic aralkyl groups having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms. Examples include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

The heterocyclic group has at least one nitrogen atom, oxygen atom and / or sulfur atom in the ring, and the size of one ring is 5 to 20 members, preferably 5 to 10 members, more preferably Is a 5- to 7-membered, saturated or unsaturated monocyclic, polycyclic or condensed ring which may be condensed with a carbocyclic group such as a cycloalkyl group, a cycloalkenyl group or an aryl group. More specifically, for example, pyridyl group, thienyl group, phenylthienyl group, thiazolyl group, furyl group, piperidyl group, piperazyl group, pyrrolyl group, morpholino group, imidazolyl group, indolyl group, quinolyl group, pyrimidinyl group, etc. Is mentioned.
The heterocyclic group may be a macrocyclic heterocyclic group such as a porphyrinyl group.
Examples of the halogen atom include chlorine, bromine, iodine, fluorine, and the like.
Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and more specifically, for example, methoxy Group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, secondary butoxy group, tertiary butoxy group, pentyloxy group, hexyloxy group, cyclopropyloxy group, cyclopentyloxy group, cyclohexyloxy Group, cyclooctyloxy group and the like.
Examples of the aryloxy group include aryloxy groups having a monocyclic, polycyclic or condensed cyclic aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms. More specifically, for example, phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group, methylnaphthyloxy group, anthryloxy group, phenanthryloxy group, biphenyloxy group and the like can be mentioned.
Examples of the alkylthio group include linear, branched, or cyclic alkylthio groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. , Methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, tertiary butylthio group, pentylthio group, hexylthio group, cyclopropylthio group, cyclopentylthio group, cyclohexylthio group, cyclooctylthio group, etc. .
Examples of the arylthio group include an arylthio group having a monocyclic, polycyclic or condensed cyclic aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and more. Specific examples include a phenylthio group, a tolylthio group, a xylylthio group, a naphthylthio group, a methylnaphthylthio group, an anthrylthio group, a phenanthrylthio group, and a biphenylthio group.
Examples of the acyl group include an acyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and more specifically, an acetyl group, a propionyl group, a butyryl group, a valeryl group, A benzoyl group, a phthaloyl group, etc. are mentioned.
Examples of the substituted silyl group include those in which 1 to 3 hydrogen atoms of the silyl group are replaced with alkyl groups, aryl groups, etc. Among them, tri-substituted products are preferable, and more specifically, trimethylsilyl groups and triethylsilyl groups. , T-butyldimethylsilyl group, triphenylsilyl group and the like.

The compound represented by the general formula (1) of the present invention can be produced according to any known method. For example, according to the method described in Patent Document 1 or Patent Document 2, an intermediate having an electron-accepting group in the group R ² or R ³ is produced, and the intermediate is produced by the method described in Patent Document 1 or Patent Document 2. It can manufacture by ring-closing according to.
Among the compounds represented by the general formula (1) of the present invention, examples of the most preferable compound include the following formula (3):

The compound represented by general formula (1) of the present invention is not limited to this.
The compound represented by the above formula (3) can also be produced according to a known method. An example of a specific method for producing the compound represented by the above formula (3) 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 biphenylacetylene derivative are reacted to produce acetylene derivative 4, and this is reacted with tetraphenylcyclopentadienone derivative to produce hexaphenylbenzene derivative 5. The acetoxy group at the end of the obtained hexaphenylbenzene derivative 5 is hydrolyzed to a hydroxy form 6, and then a TNF carboxylic acid is coupled in the presence of DCC to produce a TNF derivative 7. The target compound 8 represented by the formula (3) can be produced by cyclizing the TNF derivative 7 in the presence of a Lewis acid according to a known method.

The compound represented by the general formula (1) of the present invention produced as described above is a hexaperihexabenzocoronene derivative having no electron-accepting group at the terminal, which has been previously reported by the present inventors. It was found that the same behavior as (HBC derivative) (see Patent Documents 1 and 2) was taken.
That is, for the formation of aggregates in a tetrahydrofuran / water mixture, gelation, micelle / vesicle formation, fiber formation, depending on the amount of water in the aqueous solution and the hydrophilicity of the side chain substituent of the HBC derivative, etc. Are observed. Although rod-like and annular micelles are also observed, when water or methanol is mixed with the tetrahydrofuran solution at different ratios, formation of aggregates is observed, and high axial ratio nanotubes are formed. Moreover, a helical ribbon structure is formed by increasing the blending ratio of water in the tetrahydrofuran solution (1 mg / 1 ml). This helical structure is thought to be formed by loosening the tube.
The formation of such a tube is a two-layered ribbon-like aggregate having a width of 20 nm due to the amphiphilicity and π-π stacking effect of the compound represented by the general formula (1) of the present invention. The ribbon is then considered to spiral around. The strength of the winding at this time is considered to be adjusted by the degree of hydration of the triethylene glycol chain in the R ² and R ³ moieties.

As an example of the compound represented by the general formula (1) of the present invention, the compound 8 represented by the formula (3) was self-assembled in a solvent and formed by self-assembly of a yellow powder. A nano-sized structure was obtained.
An electron microscopic image (SEM) of the obtained yellow precipitate is shown in FIG. The lower bar on the right side of FIG. 1 shows a scale of 100 nm. As a result, this structure was found to be a nanotube having a uniform diameter (about 16 nm).
From this, it was found that the compound represented by the general formula (1) of the present invention can form a supramolecular nanotube having an electron-accepting group in the molecule.
Next, the characteristics of the supramolecular nanotube formed by the compound represented by the general formula (1) of the present invention were examined.
A sample for electrical measurement was produced using supramolecular nanotubes, which are nano-sized structures formed by self-assembly of the obtained yellow powder. Current-voltage characteristics were measured in the dark state and under light irradiation, with a delay time of 1 second after voltage application at intervals of 0.05 V from 0 V to 2 V or -2 V. The results are shown in FIG. The horizontal axis of the graph in FIG. 2 indicates the applied voltage (V), and the vertical axis indicates the current (nA) that flows. The black line in FIG. 2 shows the measurement result in the dark state, and the white line shows the measurement result under light irradiation. As a result, in the dark state, current does not flow regardless of the applied voltage, and the characteristics as an insulator are shown. However, ohmic current-voltage characteristics are exhibited under light irradiation, and 0.07 pA (dark state) at an applied voltage of 2 V. It was confirmed that the current value increased by 60,000 times from 4 to 4.2 nA (during light irradiation).
Furthermore, the switching characteristic of the current accompanying ON / OFF of light irradiation was examined. The applied voltage was 2 V, light of 60 mW was repeatedly turned off / on every minute, and the current value was recorded every second. The results are shown in FIG. The horizontal axis of the graph in FIG. 3 indicates time (minutes), and the vertical axis indicates the current (nA) that flows. As a result, a change in current value was observed with high reproducibility as the light was turned on / off.

Thus, the nano-sized structure formed by the self-assembly of the compound represented by the general formula (1) of the present invention can form supramolecular nanotubes. And the said nanotube shows photoresponsiveness. This is because when the supramolecular nanotube is irradiated with light, the excited electrons are trapped in the TNF site as an electron acceptor, and charge carriers (holes) move smoothly in the HBC column, thereby exhibiting photoconductive characteristics. It is considered a thing. As described above, the material of the present invention has a hydrophilic part necessary for forming a supramolecular nanotube, a part having a π-π stacking effect, and a function of electron accepting. A material characterized by the fact that an independent supramolecular nanotube having a diameter of about 20 nm formed by self-assembly has a function of photoconductivity is provided for the first time by the present invention.
Therefore, the present invention provides a photoconductive material comprising a nano-sized structure formed by self-assembly of the present invention, preferably a supramolecular nanotube, and the photoconductive material of the present invention is novel. 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, nanodevices, solar cell materials, field effect transistor materials, and the like.

The present invention provides a novel hexaperihexabenzocoronene derivative capable of forming a self-assembled nano-aggregate having an electron-accepting group in the molecule. The hexaperihexabenzocoronene derivative of the present invention has hydrophilic and hydrophobic substituents and can only self-assemble through amphiphilic properties and π-π stacking effects to form supramolecular nanotubes. In addition, the present invention provides a novel element material having photoresponsiveness and photoresponsiveness.
The supramolecular nanotube of the present invention is not only applied to many electronic component materials as a photodetection element, an optical switching element, a photoresponsive charge transport element, etc., but also has a novel functionality of various electronic materials using light. An element can be provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.

(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 water, and dried over anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel chromatography (CH ₂ Cl ₂ / MeOH) to obtain Compound 1 as a colorless oil (6.67 g, yield 82.24%).

(2) Synthesis of Compound 2 Under an argon atmosphere, Compound 1 (6.00 g, 19.71 mmol) obtained above and 4-bromo-4′-hydroxybiphenyl (4.46 g, 17.92 mmol) were dried in THF ( 100 ml) and 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 dichloromethane. The organic layer was washed with water, then hydrochloric acid (0.5N), water, and 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 = 8.5 Hz, 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, the obtained 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 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, then with water, and 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 = 9.0 Hz, 2H), 7.452 (d, J = 9.0 Hz, 2H),
7.387 (d, J = 9.0 Hz, 2H), 6.963 (d, J = 9.0 Hz, 2H),
4.211 (t, J = 5.0 Hz, 2H), 4.156 (t, J = 5.0 Hz, 2H),
3.865 (t, J = 5.0 Hz, 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) obtained above, 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 acetylene dissolved in benzene (25 ml) (2.06 g, 7.64 mmol) was added dropwise, and the mixture was stirred with heating 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 = 8.0 Hz, 4H), 7.526 (m, 8H), 6.982 (d, J = 8.0 Hz, 4H),
4.219 (t, J = 4.5 Hz, 2H), 4.168 (t, J = 4.5 Hz, 4H),
3.873 (t, J = 5.0 Hz, 4H), 3.690 (m, 13H), 3.539 (t, J = 5.0 Hz, 2H),
3.366 (s, 3H), 2.057 (s, 3H);
MALDI-TOF-MS: m / z:
As C ₄₁ H ₄₆ O ₉ Calcd: [M] ⁺ 682.3;
Actual value: 682.4.

(5) Synthesis of Compound 5 Compound 4 (1.00 g, 1.46 mmol) and cyclopentadiene (1.06 g, 1.46 mmol) obtained above were dissolved in diphenyl ether (4 ml) under an argon atmosphere at 350 ° C. And stirred 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 = 8.0 Hz, 4H), 7.047 (d, J = 8.0 Hz, 4H), 6.830 (m, 18H),
6.662 (d, J = 8.0 Hz, 4H), 6.610 (d, J = 8.0 Hz, 4H),
4.195 (t, J = 4.5 Hz, 2H), 4.090 (t, J = 4.5 Hz, 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 = 7.0 Hz, 6H);
MALDI-TOF-MS: m / z:
As C ₉₃ H ₁₁₅ O _9, calculated ^{values: [M + H] + 1375.8} ;
Actual value: 1375.5:

(6) Synthesis of Compound 6 Compound 5 (300 mg, 0.22 mmol) obtained above was dissolved in methanol (20 ml) and THF (10 ml), and potassium hydroxide (002 g, 0.33 mmol) was dissolved in water (1 ml). The solution dissolved in was added 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), 6.828 (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 (HPB-TNF) Under an argon atmosphere, Compound 6 (270 mg, 0.20 mmol) obtained above and 4-dimethylaminopyridine (12 mg, 0.1 mmol) were dried at room temperature with CH ₂ Cl ₂ and TNF (109 mg, 0.30 mmol) dissolved in THF (5 ml) was added and stirred for 10 minutes, followed by dicyclohexylcarbodiimide (DCC) (83 mg, 0.40 mmol) dissolved in CH ₂ Cl ₂ (5 ml). ) Was added and stirred for 2 days. After the solvent was distilled off, the residue was purified by silica gel chromatography (CH ₂ Cl ₂ / acetone) and medium pressure liquid chromatography (CH ₂ Cl ₂ / acetone) to obtain Compound 7 as a brown solid (150 mg, yield 44). %).
¹ H NMR (500 MHz, CDCl ₃ ) δ:
8.781 (d, J = 1.0 Hz, 1H), 8.723 (d, J = 1.0 Hz, 1H),
8.670 (d, J = 1.0 Hz, 1H), 8.644 (d, J = 1.0 Hz, 1H),
7.310 (d, J = 9.0 Hz, 2H), 7.195 (d, J = 8.5 Hz, 2H),
7.065 (d, J = 8.5 Hz, 2H), 6.942 (d, J = 8.5 Hz, 2H), 6.826 (m, 16H),
6.667 (m, 6H), 6.611 (d, 4H), 4.571 (t, 2H), 4.071 (t, 2H),
4.004 (t, 2H), 3.828 (m, 7H), 3.723 (s, 4H), 3.694 (m, 2H),
3.622 (m, 4H), 3.507 (t, 2H), 3.334 (s, 3H),
2.321 (t, J = 7.5 Hz, 4H), 1.370 (m, 4H), 1.236 (m, 32H),
1.071 (b, 4H), 0.859 (t, J = 7.0 Hz, 6H);
MALDI-TOF-MS: m / z:
As C ₁₀₅ H ₁₁₆ N ₃ O ₁₆ , calculated: [M + H] ⁺ : 1674.8;
Actual value: 1675.1.

(8) Synthesis of Compound 8 (HBC-TNF) Compound 7 (150 mg, 0.09 mmol) obtained above was dissolved in dry CH ₂ Cl ₂ (60 ml), and the solution was bubbled with dry argon for 10 minutes. Then, iron (III) chloride dissolved in MeNO ₃ (5 ml) was added, and the mixture was further stirred for 2 hours. The reaction mixture was poured into methanol (200 ml) with stirring, and the precipitated solid was collected by filtration, purified by silica gel column chromatography (CHCl ₃ / THF), further dissolved in chloroform, and purified by reprecipitation into methanol. Filtration gave 8 as a black solid (143 mg, 96% yield).
¹ H NMR (500 MHz, d ₈ -THF) δ:
8.335 (m, 8H), 8.159 (m, 3H), 7.965 (s, 1H), 7.721 (m, 3H),
7.570 (m, 3H), 7.399 (b, 1H), 7.303 (b, 1H), 7.127 (b, 2H),
7.070 (b, 2H), 6.685 (b, 1H), 4.335 (b, 2H), 4.295 (b, 2H),
4.237 (b, 2H), 3.952 (m, 4H), 3.766 (m, 4H), 3.664 (m, 8H),
3.510 (b, 2H), 3.346 (s, 3H), 2.991 (b, 4H), 1.993 (b, 4H),
1.580 (b, 4H), 1.300 (b, 32H), 0.873 (b, 6H);
MALDI-TOF-MS: m / z:
As C ₁₀₅ H ₁₀₄ N ₃ O ₁₆ , calculated: [M + H] ⁺ 1662.7;
Actual value: 1662.7.

Self-assembly of Compound 8 1 mg of the obtained Compound 8 (HBC-TNF) was dissolved in 5 ml of THF (0.12 mM), and 7.5 ml of MeOH was mixed at room temperature by a vapor diffusion method. About 5 days after placement, a yellow suspension was formed. A yellow powder was obtained by suction filtration.

Structure of self-assembled material An electron microscopic image (SEM) of the yellow precipitate obtained above is shown in FIG. As a result, it can be seen that nanotubes having a uniform diameter (about 16 nm) are generated.

Photoconductivity measurement A THF-MeOH solution containing HBC-TNF nanotubes on a titanium-gold electrode (interelectrode distance 3 μm, electrode length 300 μm, electrode width 8 μm) formed on a Si substrate having a 300 nm SiO ₂ insulating film. Was added dropwise and dried to prepare a sample for electrical measurement.
Current-voltage characteristics are measured from 0V to 2V or -2V at 0.05V intervals with a delay time of 1 second after voltage application, dark state and under light irradiation (Xe light source, wavelength 350-750nm, light intensity 410 mW). The results are shown in FIG. As a result, while it is a characteristic as an insulator in the dark state, it exhibits an ohmic current-voltage characteristic under light irradiation, from 0.07 pA (dark state) to 4.2 nA (during light irradiation) at an applied voltage of 2 V. And an increase in current value as much as 60,000 times.
As for the switching characteristics of the current accompanying the ON / OFF of light, the light was repeatedly turned OFF / ON every minute, and the current value was recorded every second (applied voltage 2 V, light amount 60 mW). The result is shown in FIG. A change in current value was observed with good reproducibility as the light was turned on and off.

  The present invention provides a supramolecular nanotube having photoconductivity, which is industrially useful as a functional molecule having a novel function, such as a photodetection element, an optical switching element, and a photoresponsive charge transport element. Because various applications such as optoelectronic device materials, nonlinear optical materials, inorganic / organic composite material mold materials, solar cell materials, and fuel cell materials are expected, not only chemical fields but also industrial fields such as electronic materials In the present invention, it has industrial applicability.

FIG. 1 is a photograph replacing supramolecular drawing formed by a scanning electron microscope (SEM) of a supramolecular nanotube formed from a hexaperihexabenzocoronene derivative of the present invention. FIG. 2 shows the current-voltage characteristics of a supramolecular nanotube formed from the hexaperihexabenzocoronene derivative of the present invention, in a dark state without light (black line in FIG. 2) and a bright state with light (white line in FIG. 2). It is a graph which shows the result measured by). FIG. 3 is a graph showing the results of measuring the current switching characteristics of the supramolecular nanotubes formed from the hexaperihexabenzocoronene derivative of the present invention by ON / OFF of light.

Claims (12)

The following general formula (1)
[Wherein, R ¹ independently represents an alkyl group, and R ² and R ³ each independently represent the following general formula (2)
—C ₆ H ₄ —O—R ⁵ — (O—R ⁶ ) _n —OR ⁴ (2)
(In the formula, —C ₆ H ₄ — represents a phenylene group, R ⁴ represents a hydrogen atom, an alkyl group, or a 4,5,7-trinitro-9-fluorenone (TNF) -2-carbonyl group , R ² and R ³ may be the same or different from each other, but at least one R ⁴ group of R ² and R ³ is a 4,5,7-trinitro-9-fluorenone (TNF) -2-carbonyl group , R ⁵ and R ⁶ each independently represent an alkylene group, and n represents a positive integer.)
X represents a hydrogen atom or an alkyl group . ]
A hexaperihexabenzocoronene derivative represented by: ^{2. The} hexaperihexabenzocoronene derivative according to claim 1, wherein R ⁵ and R ⁶ in R ² and R ³ of the general formula (1) are each independently an ethylene group (—CH ₂ CH ₂ —). The hexaperihexabenzocoronene derivative according to claim 1 or 2 , wherein R ^{1 in the} general formula (1) is independently an alkyl group having 10 to 30 carbon atoms. In the general formula (1), at least one of R ² and R ³ is represented by the following formula: —C ₆ H ₄ —OCH ₂ CH ₂ — (OCH ₂ CH ₂ ) _n —OCO-TNF
(In the formula, —C ₆ H ₄ — represents a phenylene group, and TNF represents a 4,5,7-trinitro-9-fluorenone (TNF) yl group.)
The hexaperihexabenzocoronene derivative according to any one of claims 1 to 3 , which is a group represented by the formula: The hexaperihexabenzocoronene derivative represented by the general formula (1) has the following formula (3)
The hexaperihexabenzocoronene derivative according to claim 4 , which is a compound represented by the formula: A nano-sized structure formed by self-assembly of the hexaperihexabenzocoronene derivative according to any one of claims 1 to 5 . The structure according to claim 6 , wherein the nano-sized structure formed by self-assembly is a nanotube. The structure according to claim 6 or 7 , wherein the structure is photoconductive. A photodetecting element comprising a nano-sized structure formed by self-assembly of the hexaperihexabenzocoronene derivative according to any one of claims 1 to 5 . Optical switching element comprising a structure of nano size formed by the self-organization of hexamethylene peri hexabenzocoronene derivative according to any one of claims 1-5. Photoresponsive charge transport element made of a structure of nano size formed by the self-organization of hexamethylene peri hexabenzocoronene derivative according to any one of claims 1-5. An electronic component material comprising at least one element according to any one of claims 9 to 11 .