JP2008266152A - Nanosize tubular self-organized body comprised of hexaperihexabenzocoronene (hbc) derivative substituted with fluorine-containing group oriented in plane direction, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nanosize tubular self-organized body obtained by self-association of a hexaperihexabenzocoronene (HBC) derivative oriented on the surface of a solution in the plane direction having a high aspect ratio and unique properties derived from a fluorine atom of its perfluoro group such as physiological activity and water/oil repellency, and a method for producing the same. <P>SOLUTION: The method for producing a nanosize tubular self-organized body oriented in the plane direction comprises causing a solution comprising at least one species of hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group having a specific structure such as 2,5-bis[4'-(perfluorohexe-1-nyloxy)phenyl]-11,14-didodecyl-hexa-peri-hexabenzocoronene to contact with vapor of a solvent other than the solvent constituting the above solution. A self-organized body produced by the above method is disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a tubular nano-sized self-assembled body in which hexaperihexabenzocoronene (HBC) derivatives substituted with a fluorine-containing group represented by the general formula (I) of the present invention are oriented in the plane direction, and It relates to a manufacturing method.

Nanoscale molecular assemblies are attracting a great deal of attention not only from basic science, but also from the application aspect of molecular devices. These molecular assemblies are expected to exhibit unique functions that reflect the characteristics and structure of the constituent molecules. Supramolecular chemistry is a promising approach to these nanoscale structures, and many attempts have been made to construct molecular assemblies with highly advanced structures.
On the other hand, among these nanoscale structures, interest in tubular materials has been increasing since the discovery of carbon nanotubes. For example, electrons such as a conductive polarizing film using carbon nanotubes (see Patent Document 1), an electronic device for connection between electrodes (see Patent Document 2), and a dispersion film used as a light emitter (see Patent Document 3) Not only as a device, but also used as an adsorbing material such as one used for hydrogen storage (see Patent Document 4) or used as a material for pistons or connecting rods (see Patent Documents 5 and 6) It is expected to be used in a wide range of fields, such as being used as a material for machine parts. The carbon nanotube is a graphene sheet structure composed of carbon atoms closed in a cylindrical shape, and is produced by evaporating the graphite material by a laser evaporation method or an arc discharge method and condensing it in the presence of a metal catalyst. There are many problems regarding processability, such as the presence of impurities such as catalyst residues and amorphous carbon, and difficulty in taking out individual tubes due to bundle formation and close entanglement. Many nanoscale tubular materials composed of inorganic materials are also known, but functional nanotubes based on organic molecules that are easy to synthesize, can be freely designed in shape and function, and are rich in processability. Development was awaited.
In fact, the formation of tubular supramolecular assemblies by self-assembly of low-molecular compounds is already known. For example, by using certain amphiphiles (lipids, oligopeptides, polymers, etc.) Or it has been reported that aggregates of other shapes are produced.

On the other hand, fluorinated carbon nanotubes are used as hydrogen storage materials for fuel cells due to their high hydrogen storage capacity, and as a raw material for sliding materials because of their good lubricity, or as cathode materials for lithium primary batteries. It is attracting a great deal of interest because it is expected to exhibit excellent properties. As a method for producing a fluorinated carbon nanotube, the above-mentioned carbon nanotube produced by evaporating a graphite material by a laser evaporation method, an arc discharge method, or the like and condensing it in the presence of a metal catalyst is used as F ₂ , ClF ₃ , A method of treating at a high temperature of 100 ° C. to 600 ° C. in an atmosphere of BrF ₃ , IF ₅ , HF, XeF ₂ , XeF ₄ , XeF ₆ or the like is known (see Patent Documents 7 to 12). It is necessary to handle poisonous gas, and the equipment is complicated and special, which is not practical. Patent Document 13 discloses a method of fluorinating carbon nanotubes at a temperature of room temperature to 250 ° C. by adjusting the fluorine gas pressure to 0.5 to 1 atm. Fluorinated carbon nanotubes are not suitable as functional materials because they are released as gas when heated to 600 ° C. Patent Document 14 proposes a method of fluorinating carbon nanotubes under irradiation with ultraviolet light having a wavelength of 200 nm or less using a perfluoroalkane solution of perfluoroazoalkane. However, unstable materials and special solvents are proposed. Further, it is not economical because a special light source such as a low pressure mercury lamp, a high pressure mercury lamp, an ArF or XeCl excimer laser, or an excimer lamp is used.
As described above, the conventional technology for fluorinating carbon nanotubes is to directly fluorinate carbon nanotubes, and the method for obtaining fluorinated nanotubes by self-assembly of fluorine-containing compounds as in the present invention is as follows. unknown.

  In addition, as for conventional carbon nanotubes, many studies on the orientation control method have been conducted. For example, a method of arranging carbon nanotubes in a groove provided on a substrate (see Patent Documents 15 and 16), carbon nanotubes as gelatin, etc. After dispersion in a transparent binder, a method of aligning by performing a wire bar coating operation on the substrate (see Patent Document 3), and a method of manufacturing carbon nanotubes arranged in parallel to the substrate on the substrate (Patent Document 17) In addition, after forming an edge extending in a plane made of step bunching on a SiC substrate having a Si surface as a main surface, the main surface is heat-treated under vacuum and oriented in a direction along this surface. A method of forming carbon nanotubes (see Patent Document 18), a plasma CVD method, etc., perpendicular to the substrate A method of inclining carbon nanotubes grown in one direction by applying mechanical stress from one direction (see Patent Document 2 and Patent Document 19), orientation means such as stretching, electric field, and magnetic field by dispersing carbon nanotubes in a polymer (Refer to Patent Document 1 and Patent Documents 20 to 25). However, these methods all require advanced substrate processing techniques and complicated processes, and more complicated operations are required to obtain a single film of oriented carbon nanotubes. Or a method for producing a composite material with a resin or the like, and there has been a problem that its use is limited. There is no known method for orienting fluorinated nanotubes or producing fluorinated nanotubes.

However, these self-assembled bodies are constructed through hydrophobic effects, intramolecular or intermolecular hydrogen bonds, etc., and those utilizing intermolecular interactions by π-π stacking as in the present invention Nothing other than what was previously proposed by the present inventors is known. (See Patent Documents 26 and 27 and Non-Patent Documents 2 and 3).
The hexaperihexabenzocoronene (HBC) molecule is a graphite partial structure, and forms a stable discotic liquid crystal phase by introducing a long-chain alkyl group or the like. However, studies related to HBC have been limited to single molecules or liquid crystal states. For example, as for hexabenzocoronene derivatives, those using hexabenzocoronene as an organic semiconductor (see Patent Documents 28 to 30), and controlling the molecular orientation by introducing perfluorocarbon groups into liquid crystalline compounds such as coronene and benzocoronene. And the like (see Patent Document 31) have been reported. However, there are almost no examples of nanostructures using HBC derivatives as motifs.

JP 2006-285068 A JP 2006-228818 A JP 2006-27961 A JP 2005-137970 A JP 2006-250280 A JP 2006-266448 A JP 2003-238133 A JP 2004-284852 A JP 2004-313906 A JP 2005-189322 A JP 2005-219950 A JP 2006-240938 A JP 2005-273070 A Japanese Patent Laid-Open No. 2005-200272 JP-A-2005-75711 JP 2005-169614 A JP 2006-026533 A JP 2004-231464 A JP 2006-11296 A JP 2002-362457 A JP 2003-3194 A JP 2004-016858 A JP 2004-087714 A JP 2005-154950 A JP 2005-161599 A Japanese Patent Laid-Open No. 2005-220046 JP-A-2005-220047 JP 2004-158709 A JP 2005-79163 A JP 2006-41495 A JP 2004-35617 A Y. Huang et al., Science 291, 630. (2001) Science, 304, 1481-1483 (2004), Proc. Natl. Acad. Sci. USA, 102, 10801-10806 (2005)

  The present invention provides a tube-shaped nano-sized self-assembled body having a large aspect ratio and a unique property derived from a fluorine atom of a bellfluor group, such as physiological activity and water / oil repellency, on the surface of a solution. Provided are a nanotube-like aggregate self-assembled and oriented in a plane direction, and a method for producing the same.

  Since most of the nanostructures reported so far are composed of amphiphilic compounds such as lipids, even if the structures are obtained, they do not exhibit any remarkable properties. In contrast, the present inventors have focused on hexaperihexabenzocoronene (HBC), which is a partial structure of graphite, as a basic element for the construction of nanostructures, and examined the development of nanostructures using HBC derivatives as motifs. I have done it. The present inventors precisely designed the balance between the hydrophilic substituent and the hydrophobic substituent to be introduced into the HBC skeleton, synthesized a novel amphiphilic HBC derivative, and investigated its association behavior. Already found to form a gel by self-association in a specific solvent, and to form a nanotube-like aggregate or ribbon-like nanostructure with a high uniform aspect ratio in the gel. (See Patent Documents 26 and 27 and Non-Patent Documents 2 and 3). The present inventors have studied to further improve the properties of the nanostructure obtained in this way. On the other hand, organic compounds containing a bellfluor group are attracting attention because they are expected to exhibit unique properties derived from fluorine atoms. In particular, bioactivity and water / oil repellency are attracting attention. If fluorine atoms can be introduced into the nanostructure, it can be expected to greatly improve the lubricity, smoothness, stability, etc. of the nanostructure surface. Succeeded in synthesizing a derivative in which a bellfluor group was introduced as a skeletal substituent, and found that the derivative self-assembled under a specific condition to form a nanotube-like aggregate oriented in the plane direction. did.

  That is, the present invention provides the following general formula (I)

(In the formula, each R ¹ independently represents a linear or branched alkyl group having 4 to 20 carbon atoms, and each R ² independently represents the following general formula (II):
—C ₆ H ₄ —O—R ³ (II)
(In the formula, R ³ represents a perfluoroalkenyl group having 4 to 30 carbon atoms, and the substitution position on the benzene ring represented by —C ₆ H ₄ — is either the ortho position, the meta position, or the para position. Indicates that.)
And each X independently represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkynyl group having 2 to 4 carbon atoms, or a substituent. A pyridyl group, a terpyridyl group which may have a substituent, or a porphyrinyl group which may have a substituent, wherein the alkynyl group, the pyridyl group, the terpyridyl group, and the porphyrinyl group have a halogen atom, The substituent selected from the group which consists of a C1-C10 alkyl group and a C6-C20 aryl group is shown. )
By bringing a vapor of another solvent different from the solvent of the solution into contact with a solution containing at least one hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by: The present invention relates to a method for forming a tubular nano-sized self-assembled body in which the compound represented by the general formula (I) is oriented in the plane direction on the surface of the solution.
Further, the present invention is a tube-like structure in which a hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by the general formula (I) that can be produced by the above-described method of the present invention is oriented in the plane direction. It relates to nano-sized self-assembly. More specifically, the present invention relates to a solution containing at least one hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by the general formula (I). A tube-shaped nano-sized self-assembled body in which the compound represented by the general formula (I) is oriented in the plane direction on the surface of the solution by contacting with the vapor of another solvent different from the solvent of the solution .

The embodiment of the present invention will be described in detail as follows.
(1) A solution containing at least one hexaperihexabenzocoronene (HBC) derivative substituted with the fluorine-containing group represented by the general formula (I) is different from the solvent of the solution. A method of forming a tube-shaped nano-sized self-assembled body in which the compound represented by the general formula (I) is oriented in the plane direction on the surface of the solution by contacting with the vapor of the solvent.
(2) A solvent for dissolving a hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by the general formula (I) is composed of dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclohexane, and methylcyclohexane. The method according to (1) above, which is one or more selected from the group.
(3) The method according to (1) or (2) above, wherein the solvent is tetrahydrofuran.
(4) The other solvent different from the solvent of the solution is the poor solvent for the hexaperihexabenzocoronene (HBC) derivative substituted with the fluorine-containing group represented by the general formula (I). The method according to any one of (3).
(5) The method according to (4), wherein the poor solvent is a hydrocarbon solvent having 5 to 12 carbon atoms.
(6) The method according to (1) to (5) above, wherein the linear or branched alkyl group having 4 to 20 carbon atoms of R ¹ in the general formula (I) is a tert-butyl group.
(7) In the above general formula (I), the linear or branched alkyl group having 4 to 20 carbon atoms of R ^{1 is} a linear or branched alkyl group having 10 to 20 carbon atoms ( The method as described in 1)-(6).
(8) The method according to any one of (1) to (7), wherein R ³ in R ² of the general formula (I) is a 1-perfluoroalkenyl group having 4 to 10 carbon atoms.
(9) The method as described in said (1)-(8) whose X in general formula (I) is a hydrogen atom or a halogen atom.
(10) A hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by the above general formula (I), which can be produced by any one of the methods (1) to (9), is a surface. Tube-shaped nano-sized self-assembled body oriented in the direction.
(11) The solution containing at least one hexaperihexabenzocoronene (HBC) derivative substituted with the fluorine-containing group represented by the general formula (I) is different from the solvent of the solution. A tube-shaped nano-sized self-assembly in which the compound represented by the general formula (I) is oriented in the plane direction on the surface of the solution by contacting with the vapor of another solvent.

The hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by the general formula (I) of the present invention is intermolecular due to the π-π stacking action by π electrons of hexaperihexabenzocoronene (HBC). This is a self-assembling molecule that utilizes interactions, and has a hydrophobic group such as a bulky alkyl group or long-chain alkyl group in the molecule, and a perfluoroalkenyloxy group that has a large number of fluorine atoms in the molecule. It is characterized by having. By such molecular design, a nanoscale self-assembled body having a very specific property having a property of a fluorine compound by a perfluor group and having a self-assembling property by π-π stacking action while maintaining hydrophobicity. Can be formed.
Therefore, the hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group of the present invention is not limited to the chemical structural formula represented by the general formula (I) described above, It has a hexabenzocoronene (HBC) skeleton, a hydrophobic group such as a bulky alkyl group or a long-chain alkyl group, and a perfluoro group having a large number of fluorine atoms. It is characterized in that it has a self-assembling property by π stacking action, and the one having these characteristics is a hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group of the present invention. Will be included.

As the linear or branched alkyl group having 4 to 20 carbon atoms of R ¹ in the general formula (I) of the present invention, a group having a large hydrophobicity is preferable. Particularly, an alkyl group having a small carbon number has a branched bulk. High groups are preferred. Preferred alkyl groups include bulky groups such as a tert-butyl group and linear or branched alkyl groups having 5 to 20 carbon atoms, preferably 10 to 20 carbon atoms such as decyl and dodecyl groups. Further, the two R ¹ groups in the general formula (I) may be the same or different, but are preferably the same group from the standpoint of production convenience.
Examples of the group represented by the general formula (II) of R ² in the general formula (I) of the present invention include a perfluoroalkenyloxyphenyl group having a perfluoroalkenyl group having 4 to 30 carbon atoms. The substitution position on the phenyl group of the perfluoroalkenyloxy group may be any of the ortho position, the meta position, and the para position, but a preferred position includes the para position. Further, examples of the perfluoroalkenyl group include linear or branched, preferably linear perfluoroalkenyl groups having 4 to 30 carbon atoms, preferably 4 to 10 carbon atoms. The number and position of the carbon-carbon double bonds of these perfluoroalkenyl groups are not particularly limited, but a 1-perfluoroalkenyl group having one carbon-carbon double bond at the 1-position is preferable. Preferred perfluoroalkenyl groups include the following general formula (III):
_{-CF = CF- (CF 2) n} -CF 3 (III)
(In the formula, n represents an integer of 1 to 22, preferably 1 to 10, more preferably 1 to 7.)
The 1-perfluoroalkenyl group represented by these is mentioned. Further, the two R ² groups in the general formula (I) may be the same or different, but are preferably the same group from the standpoint of production convenience.

Examples of the halogen atom of X in the general formula (I) of the present invention include halogen atoms such as a chlorine atom, a bromine atom, or an iodine atom. Examples of the alkynyl group having 2 to 4 carbon atoms include linear or branched alkynyl groups having 2 to 4 carbon atoms such as an ethynyl group. As a pyridyl group, any of 2-pyridyl group, 3-pyridyl group, or 4-pyridyl group may be sufficient. The terpyridyl group may be a monovalent group derived from terpyridine bonded with three pyridines, but is preferably a dipyridylpyridyl group consisting of a pyridyl group at the center. The porphyrinyl group may be a monovalent group derived from porphyrin, and preferably a group that binds to the pyrrole ring of porphyrin.
These alkynyl group, pyridyl group, or porphyrinyl group are a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom; a linear or branched alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group; In addition, the aryl group may be substituted with one or more substituents selected from the group consisting of monocyclic, polycyclic, or condensed cyclic aryl groups having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group.
Further, the two X groups in the general formula (I) may be the same or different, but are preferably the same group from the standpoint of production.

The hexaperihexabenzocoronene (HBC) derivative substituted with the fluorine-containing group of the present invention can be produced according to the methods described in Patent Documents 26 and 27. In a more specific method for producing the compound of the present invention, R ¹ in the general formula (I) is a dodecyl group (—C ₁₂ H ₂₅ group), and R ² is -4-C ₆ H ₄ —O—CF. = CF-C ₄ F ₉ group, and the compound in which X is a hydrogen atom will be described as an example. This production example is shown by the following chemical reaction formula.

First, compound 1 is reacted with an acetylene derivative in the presence of a copper catalyst to produce biphenylacetylene derivative 2.
After lithiation of 4-dodecyl bromobenzene 3, this is reacted with 1,4-dimethylpiperazine-2,3-dione to form a diketone body 4, which is reacted with dibensyl ketone to give a tetraphenylcyclopentadienone derivative 5 Then, this is reacted with the biphenylacetylene derivative 2 produced previously to obtain a hexaphenylbenzene derivative 6.
Next, the terminal methoxy protecting group of the biphenyl group is hydrolyzed to give a free hydroxyl group derivative 7, which is reacted with perfluoroalkylene in the presence of a base to give a perfluoroalkenyloxy derivative 8, which is the presence of an iron catalyst. The target compound 9 can be prepared by cyclization below.
The method described here is an example, and the method for producing a hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group of the present invention is not limited to this method, and various methods according to this method. Can be manufactured.

Next, the hexaperihexabenzocoronene (HBC) derivative (hereinafter, simply referred to as HBC derivative) substituted with the fluorine-containing group of the present invention produced in this manner is prepared by placing the HBC derivative of the present invention in a solvent. This is heated to dissolve. The self-assembled body of the present invention can be produced by mixing and stirring the resulting solution with an ultrasonic mixer until it is suspended, and aging this at room temperature. However, the fluorinated nanotubes of the present invention have a specific structure with a large aspect ratio and are preferably oriented in one direction in order to effectively bring out their properties. It was difficult to arrange in one direction. In order to arrange this in one direction, the present invention is not a forced mixing and stirring, but a method of manufacturing a self-assembly that is aligned in the plane direction with the surface of the solution using two or more solvents. Is to provide.
In the method for producing a self-assembled body of the present invention, first, the HBC derivative of the present invention is placed in a solvent, and if necessary, this is heated and dissolved. Next, the solution is allowed to stand, and the surface of the solution is brought into contact with a vapor of another solvent different from the solvent of the solution, so that the HBC derivative of the present invention is oriented in the plane direction on the surface of the solution. Forming a nano-sized self-assembled body. To illustrate the preferred method of the present invention, the solution of the HBC derivative of the present invention is cooled to room temperature, and this solution is put together with the glass container into a second glass container larger than the glass container without a lid, Another solvent different from the solvent of the solution, preferably a poor solvent, is placed in the second glass container. Then, the outer second glass container is sealed, the poor solvent vapor is diffused and brought into contact with the HBC derivative solution of the present invention, and the inner solution is aged for about one week at room temperature. A yellow transparent film is formed on the surface. An outline of this method is schematically shown in FIG. First, a small glass container containing a solution of the HBC derivative of the present invention is placed in a large glass container, a poor solvent of the HBC derivative of the present invention is placed in a large glass container, and the vapor of the poor solvent is brought into contact with the surface of the solution. . As a result, self-assembled bodies are formed in alignment on the solution surface.

The solvent for the solution for dissolving the HBC derivative of the present invention may be any solvent that can be heated to dissolve the HBC derivative of the present invention. Preferred solvents include dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclohexane. And methylcyclohexane. More preferred solvent is tetrahydrofuran. The amount of the solvent to be used is an amount that can be dissolved by heating, and can be such that no self-assembly is formed even at room temperature. For example, the HBC derivative of the present invention by weight with respect to 1 mL of the solvent. However, about 0.1 to 5 mg, preferably about 0.5 to 5 mg, and about 0.5 to 2 mg can be mentioned.
The temperature to be heated may be a temperature at which a transparent solution is obtained by dissolution, and may be equal to or lower than the boiling point of the solvent. As preferable temperature, 35-80 degreeC and about 40-70 degreeC are mentioned. For example, when dichloromethane or tetrahydrofuran (THF) is used as the solvent, the temperature is preferably about 40 ° C to 66 ° C.
As another solvent different from the solvent of the solution, a poor solvent that cannot sufficiently dissolve the HBC derivative of the present invention is preferable. As such a poor solvent, for example, a hydrocarbon solvent having 5 to 12 carbon atoms such as n-hexane, preferably an aliphatic saturated hydrocarbon having 5 to 12 carbon atoms, more preferably 5 to 8 carbon atoms. A solvent is mentioned.
Although the room temperature is preferable as the temperature to be allowed to stand (aging temperature), it is not limited to this, and cooling or heating may be performed according to the solubility and vapor pressure of the solvent used.
The time of standing (ripening time) is until a sufficient self-assembly is formed on the surface of the solution, and is not particularly limited, but usually a film is formed in about one week.

A field emission scanning electron microscope (FE-SEM) photograph of the self-assembled body of the present invention thus obtained is shown in FIG. 2 as a photograph replacing the drawing. The left and right sides of FIG. 2 are 50,000 times photographs, and the bar indicates 100 nm. Further, a transmission electron microscope (TEM) photograph is shown in FIG. 3 as a photograph replacing the drawing. The left bar in FIG. 3 indicates 100 nm, and the right bar indicates 50 nm.
As a result of these observations, it was found that the self-assembled body of the present invention was produced as a nano-sized tube having a large aspect ratio and a narrow wire diameter distribution. Although this tube has traces of a helical structure and some are curved, it is a somewhat rigid tube, and this structure is a two-dimensional structure due to the interaction between the π-π interaction and the alkyl group. Formation of a molecular film-like structure, which forms a self-assembly that spreads two-dimensionally and is aligned in the plane direction by the surface of the solution, and further forms a tube structure by packing it closely in a coil shape Hierarchical self-organization has created a double-layered tube, indicating that perfluoroalkyl chains are present on the surface of the inner and outer layers of the tube. These results are also shown by the infrared absorption spectrum.

The self-assembly of the present invention has a perfluoroalkyl chain and is not only aligned in the plane direction but also exhibits super water repellency.
Therefore, the self-assembled body of the present invention is a nanoscale structure based on the interaction between the π-π stacking action and the hydrophobic alkyl group, and is suitable as an adsorbing material such as a hydrogen gas storage agent or a catalyst carrier. In addition, it can also be applied to nanodevices such as sensors, inorganic organic composite material templates, molecular wires, nonlinear optical materials, lithium battery electrodes, solar cell materials, fuel cell materials, etc. Not only that, but because of the introduction of perfluoroalkyl groups, it exhibits super water repellency and can be formed into a film shape to roofs, antennas, cables, steel towers, tools for civil engineering machinery, shelves in warehouses for freezing, etc. As an anti-adhesion agent and snow-prevention agent for automobiles, window glass, mirror glass, decorative glass for interior and exterior for vehicles, ships, aircraft, and buildings, etc. As a water and oil repellent and antifouling film for seed building materials and building materials, and further to surface treatment agents such as plastic films, plastic moldings, glass, ceramics, metals, paper, and fibers, and marine organism adhesion prevention agents. It is a material suitable for the application.

HBC, which is the basic skeleton of the compound of the present invention, is an extremely hydrophobic molecule that is regarded as a graphite fragment. However, by introducing a fluor group, the hydrophobic effect and the π-π stacking due to the overlap of the molecular planes are combined. Self-assembly through effects can form nanoscale tubular or fiber-like assemblies. In particular, the nanotubes formed in this way not only have the same properties as the nanotubes derived therefrom due to their structural relevance to the nanotubes generated from graphite, but also through the overlap of HBC-specific π electrons. Expected to have electronic properties that are not found in conventional nanotubes, such as smooth carrier movement, from lipids, etc., and also has features such as being free of impurities such as metals and having a large aspect ratio and uniform thickness. In addition, the HBC derivative of the present invention also has physiological activity derived from fluorine atoms and water / oil repellency.
Moreover, according to the present invention, there is an advantage that a fluorinated nanotube can be easily produced under mild conditions without using a harmful gas such as fluorine gas, and the fluorine content can be designed freely. Moreover, a super-water-repellent surface can be easily produced by casting the produced suspension of fluorinated nanotubes to a desired surface.
Furthermore, the self-assembled body of the present invention is oriented in one direction in the plane direction, and the characteristics of the self-assembled body described above can be extracted more effectively.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.
In the following Examples and Comparative Examples, commercially available reagents and solvents were used as they were unless otherwise specified.
¹ H-NMR and ¹³ C-NMR spectra were measured at 500 MHz and 125 MHz, respectively, using a JEOL NM-Excalibur500 model, with the non-deuterated solvent remaining in the deuterated solvent as an internal standard.
The infrared absorption spectrum was measured using a JASCO-V570DS ultraviolet visible near infrared spectrophotometer.
Mass spectrometry was performed using an Applied Biosystems BioSpectrometry Workstation model Voyager-DE STR spectrometer and dithranol as a matrix.
Scanning electron micrographs were taken at 5 kV using a JEOL JSM-6700F FE-SEM.
Transmission electron micrographs were taken at 120 kV using a Philips model Tecnai F20 electron microscope.

2,5-bis [4 ′-(perfluorohex-1-yloxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) (R ¹ in the above general formula (I) is dodecyl Group (—C ₁₂ H ₂₅ group), wherein R ² is a -4-C ₆ H ₄ —O—CF═CF—C ₄ F ₉ group and X is a hydrogen atom) Manufacturing

(1) Preparation of 1,2-bis (4′-methoxy-4-biphenylyl) ethyne (2) 4-Bromo-4-methoxybiphenyl (1) (2.7 g, 10.12 mmol), 1,8-diazabicyclo [5 , 4,0] -7-undecene (DBU) (9.2 g, 60.43 mmol), PdCl ₂ (PPh ₃ ) ₂ (425 mg, 0.61 mmol), and cuprous iodide (CuI) (191 mg, 1.00 mmol). Dissolved in benzene (20 ml), trimethylsilylacetylene (0.71 ml, 496 mg, 5.05 mmol) and water (70 μl) were added successively. This mixed solution was heated to 60 ° C. and kept for 24 hours. The formed precipitate was separated by filtration, washed with ice-cooled dichloromethane, and then recrystallized from toluene to obtain the desired 1,2-bis (4′- Methoxy-4-biphenylyl) ethyne (2) was obtained as light brown crystals.
Yield: 1.4 g (3.51 mmol), yield: 69%.
¹ H-NMR (500 MHz, THF-d ₈ ): δ
7.56 (t, J = 8.5 Hz, 8H), 7.50 (d, J = 8.5 Hz, 4H),
6.93 (d, J = 8.5 Hz, 4H), 3.76 (s, 6H).
MALDI-TOF-MS: As C ₂₈ H ₂₂ O ₂
Calculated value [M + H] ⁺ : m / z = 390.47;
Measurement value: 390.13.

(2) Production of 3,4-di (4-dodecylphenyl) -2,5-diphenylcyclopentadien-1-one (5) 1,2-bis- (4-dodecylphenyl) -1,2-diketone ( 4) was prepared by the method described in the literature (S. Ito et al., Chem. Eur. J. 6, 4327 (2000)).
1,2-bis- (4-dodecylphenyl) -1,2-diketone (4) (1.5 g, 2.75 mmol) and dibenzyl ketone (0.58 g, 2.76 mmol) are dissolved in dioxane and heated to 100 ° C. Tetrabutylammonium hydroxide (1.0 M 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. The extract was evaporated to dryness and purified by silica gel column chromatography [eluent: dichloromethane / hexane (concentration gradient: 10-50% dichloromethane)]. Further purification by preparative HPLC, eluting with dichloromethane / hexane (1: 3), evaporated to dryness to remove the solvent and 2,5-diphenyl-3,4-bis (4-dodecylphenyl) cyclopentadienone (5) was obtained as a purple powder.
Yield: 0.88 g, yield: 44%.
¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.24 (m), 6.96 (d, J = 7.94Hz, 4H), 6.80 (d, J = 7.94Hz, 4H),
2.55 (t, J = 7.63Hz, 4H), 1.56 (br., 4H), 1.26 (br., 36H),
0.88 (t, J = 6.71Hz, 6H).
MALDI-TOF (dithranol): m / z = 720 (M ⁺ ).

(3) Production of 2,3-bis (4′-methoxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (6) Manufactured in (2) described above 3,4-di (4-dodecylphenyl) -2,5-diphenylcyclopentadien-1-one (5) (6.7 g, 9.22 mmol) and 1,2-bis (4 prepared in (1) above '-Methoxy-4-biphenylyl) ethyne (2) (3.6 g, 9.22 mmol) was suspended in diphenyl ether (10 ml) in Schlenk, refluxed (˜300 ° C.) for 24 hours, and then cooled to room temperature. Ethanol (300 ml) was added to the reaction mixture, and the resulting brown precipitate was separated by filtration and purified by silica gel column chromatography (eluent: ethyl acetate / hexane (7/1)). -Bis (4'-methoxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (6) was obtained as a colorless solid.
Yield: 8.0 g (7.38 mmol), yield: 80%.
¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.34 (d, J = 8.5 Hz, 4H), 7.06 (d, J = 7.5 Hz, 4H), 6.89-6.80 (m, 18H),
6.68 (d, J = 8.0 Hz, 4H), 6.62 (d, J = 8.0 Hz, 4H), 3.77 (s, 6H),
2.33 (t, J = 7.5 Hz, 4H), 1.41-1.35 (m, 4H), 1.31-1.20 (m, 32H),
1.09 (br., 4H), 0.87 (t, J = 7.5 Hz, 6H).
¹³ C-NMR (125 MHz, CDCl ₃ ): δ
158.69, 140.77, 140.59, 140.34, 139.68, 139.19, 137.82, 136.83, 133.31,
131.83, 131.46, 131.18, 127.60, 126.50, 126.48, 124.91, 124.59, 113.90,
55.34, 35.38, 32.01, 32.00, 31.23, 29.81, 29.76, 29.60, 29.46, 28.88,
22.79, 14.21.
MALDI-TOF-MS: as C ₈₀ H ₉₀ O ₂
Calculated value [M + H] ⁺ : m / z = 1083.57;
Measurement value: 1083.81.

(4) Production of 2,3-bis (4′-hydroxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (7).
As described above (2,3-bis (4′-methoxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (6) prepared in 3) (8.0 g, 7.38 mmol Boron tribromide (BBr ₃ ) (2.6 ml, 27.5 mmol) was added to the dichloromethane solution at 0 ° C. and stirred for 45 minutes at 0 ° C. and then overnight at room temperature The reaction mixture was mixed with ice water / tetrahydrofuran. The extract was washed with brine, dried over anhydrous magnesium sulfate and evaporated to dryness on a rotary evaporator, and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / Hexane (7/1)) and purified by 2,3-bis (4′-hydroxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylben Down the (7) was obtained as a colorless solid.
Yield: 7.0 g (6.63 mmol), yield: 90%.
¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.28 (d, J = 8.5 Hz, 4H), 7.04 (d, J = 8.5 Hz, 4H), 6.89-6.79 (m, 14H),
6.75 (d, J = 8.5 Hz, 4H), 6.67 (d, J = 8.5 Hz, 4H),
6.61 (d, J = 8.0 Hz, 4H), 2.33 (t, J = 7.5Hz, 4H), 1.40-1.35 (m, 4H),
1.30-1.19 (m, 34H), 1.08 (br., 4H), 0.87 (t, J = 7.5 Hz, 6H).
¹³ C-NMR (125 MHz, CDCl ₃ ): δ
154.58, 140.75, 140.60, 140.33, 139.64, 139.24, 139.20, 137.80, 136.77,
133.53, 131.82, 131.44, 131.16, 127.84, 126.49, 126.47, 124.91, 124.57,
115.30, 35.37, 32.00, 31.22, 29.80, 29.75, 29.59, 29.45, 28.87, 22.77,
14.20.
MALDI-TOF-MS: as C ₉₀ H ₈₄ F ₂₂ O ₂
Calculated value [M + H] ⁺ : m / z = 1614.61;
Measurement: 1614.75.

(5) Production of 2,3-bis [4 ′-(perfluorohex-1-yloxy) -4-biphenylyl] -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (8) .
2,3-bis (4′-hydroxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (7) prepared in the above (4) (200 mg, 0.19 mmol) To a solution of potassium and potassium carbonate (200 mg) in dry tetrahydrofuran (5 ml), excess perfluoro-1-hexene (0.3 ml) was continuously added with a syringe, and the resulting suspension was stirred at room temperature for 25 hours under an argon atmosphere. did. The reaction mixture was evaporated to dryness and the residue was extracted with dichloromethane / water. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and evaporated to dryness on a rotary evaporator. The residue was purified by silica gel column chromatography (eluent: dichloromethane / hexane (8/1)), and 2,3-bis [4 ′-(perfluorohex-1-yloxy) -4-biphenylyl] -5,6 -Di (4-dodecylphenyl) -1,4-diphenylbenzene (8) was obtained as a colorless solid.
Yield: 180 mg, yield: 59%.
¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.42-7.39 (m, 4H), 7.15-7.02 (m, 8H), 6.91-6.81 (m, 14H),
6.68-6.62 (m, 8H), 4.10-4.08 (m, 4H), 3.84-3.81 (m, 4H),
3.74-3.59 (m, 14H), 3.53-3.51 (m, 2H), 3.34 (s, 3H), 2.32 (t, J = 7.5Hz, 4H),
1.40-1.34 (m, 4H), 1.29-1.19 (m, 32H), 1.07 (br, 4H),
0.86 (t, J = 7.0Hz, 6H).
_{MALDI-TOF-MS:} calculated for _{C 90 H 84 F 22 O 2} [M + H] +: m / z = 1614.61;
Measurement: 1614.75.

(6) Production of 2,5-bis [4 ′-(perfluorohex-1-yloxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) 2 produced in (5) above , 3-bis [4 '-(perfluorohex-1-yloxy) -4-biphenylyl] -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (8) (180 mg, 0.11 mmol) Solution of ferric chloride (FeCl ₃ ) (542 mg, 3.34 mmol) in nitromethane (MeNO ₂ ) (3.5 ml) was slowly added under an argon atmosphere. The mixture was reacted for 1 hour at 25 ° C. with stirring, and the reaction solution was poured into 200 ml of methanol. The produced precipitate was separated by filtration and subjected to silica gel column chromatography (eluent: hot tetrahydrofuran) to collect a yellow fraction. The residue obtained by evaporation to dryness of this fraction was recrystallized from tetrahydrofuran to obtain the desired 2,5-bis [4 ′-(perfluorohex-1-yloxy) phenyl] -11,14-didodecyl-hexa. -Peri-hexabenzocoronene (9) was obtained as yellow crystals.
Yield: 140 mg, yield: 78%.
¹ H-NMR (500 MHz, THF-d ₈ , 55 ° C.): δ
7.66-6.92 (m, 22H), 2.65 (br, 4H), 1.73 (br, 4H), 1.47-1.09 (m, 36H),
0.83 (br, 6H).
MALDI-TOF-MS: as C ₉₀ H ₇₂ F ₂₂ O ₂
Calculated value [M + H] ⁺ : m / z = 1602.52;
Measurement value: 1602.64.

Self-assembly method of HBC derivatives (see Fig. 1)
In a glass container, 1 mg of 2,5-bis [4 ′-(perfluorohex-1-yloxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) prepared in Example 1 was placed. Was added to 1 mL of tetrahydrofuran and heated to 40 ° C. to obtain a transparent solution. Then, this solution was put together with the glass container into a second glass container sufficiently larger than the glass container without a lid, and 2 ml of n-hexane was added to the second glass container on the outside. When the outer second glass container was sealed and aged at room temperature for one week, a yellow film was formed on the inner liquid surface. After copying this film onto a silicon substrate or the like, it was observed with a field emission scanning electron microscope (FE-SEM) and a transmission electron microscope (TEM). As a result, a nano-sized tube with a large aspect ratio and a narrow wire diameter distribution was found. They were generated in one direction parallel to the film surface.
FIG. 2 shows an FE-SEM image of the tube, and FIG. 3 shows a TEM photograph of the tube.

  The present invention provides self-assembled and unidirectionally aligned nanoscale self-assemblies, and the nanoscale self-assemblies of the present invention are structurally related to nanotubes formed from graphite. In addition to having the same properties as nanotubes derived from HBC, electronic properties that are not found in conventional nanotubes from lipids, such as smooth carrier movement through the π-electron overlap peculiar to HBC, are expected, It does not contain impurities such as metals, has features such as a large aspect ratio and uniform thickness, and the HBC derivative of the present invention also has physiological activity derived from fluorine atoms and water and oil repellency. It is not only useful for various adsorbing materials and electronic devices as a nanomaterial having water repellency, but also because it has super water repellency. It is also useful as a surface treatment material for various vehicles, marine, aircraft, and building materials as an anti-adhesion material for snow, an adhesion prevention material for snow and water, and has industrial applicability. .

FIG. 1 schematically shows a method for producing a self-assembly according to the present invention. FIG. 2 is a photograph replacing a drawing showing an FE-SEM image of the self-assembled body of the present invention produced in Example 2. FIG. 3 is a photograph replacing a drawing showing a TEM photograph of the self-assembled body of the present invention produced in Example 2.

Claims (6)

The following general formula (I)
(In the formula, each R ¹ independently represents a linear or branched alkyl group having 4 to 20 carbon atoms, and each R ² independently represents the following general formula (II):
—C ₆ H ₄ —O—R ³ (II)
(In the formula, R ³ represents a perfluoroalkenyl group having 4 to 30 carbon atoms, and the substitution position on the benzene ring represented by —C ₆ H ₄ — is either the ortho position, the meta position, or the para position. Indicates that.)
And each X independently represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkynyl group having 2 to 4 carbon atoms, or a substituent. A pyridyl group, a terpyridyl group which may have a substituent, or a porphyrinyl group which may have a substituent, wherein the alkynyl group, the pyridyl group, the terpyridyl group, and the porphyrinyl group have a halogen atom, The substituent selected from the group which consists of a C1-C10 alkyl group and a C6-C20 aryl group is shown. )
By bringing a vapor of another solvent different from the solvent of the solution into contact with a solution containing at least one hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by: A method of forming a tubular nano-sized self-assembled body in which the compound represented by the general formula (I) is oriented in the plane direction on the surface of the solution.   The solvent for dissolving the hexaperihexabenzocoronene (HBC) derivative substituted with the fluorine-containing group represented by the general formula (I) is selected from the group consisting of dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclohexane, and methylcyclohexane The method of Claim 1 which is 1 type, or 2 or more types.   The method according to claim 1 or 2, wherein the solvent is tetrahydrofuran.   The other solvent different from the solvent of the solution is a poor solvent for a hexaperihexabenzocoronene (HBC) derivative substituted with a fluorine-containing group represented by the general formula (I). The method described in 1.   The method according to claim 4, wherein the poor solvent is a hydrocarbon solvent having 5 to 12 carbon atoms. The following general formula (I) which can be produced by the method according to claim 1.
(In the formula, each R ¹ independently represents a linear or branched alkyl group having 4 to 20 carbon atoms, and each R ² independently represents the following general formula (II):
—C ₆ H ₄ —O—R ³ (II)
(In the formula, R ³ represents a perfluoroalkenyl group having 4 to 30 carbon atoms, and the substitution position on the benzene ring represented by —C ₆ H ₄ — is either the ortho position, the meta position, or the para position. Indicates that.)
And each X independently represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkynyl group having 2 to 4 carbon atoms, or a substituent. A pyridyl group, a terpyridyl group which may have a substituent, or a porphyrinyl group which may have a substituent, wherein the alkynyl group, the pyridyl group, the terpyridyl group, and the porphyrinyl group have a halogen atom, The substituent selected from the group which consists of a C1-C10 alkyl group and a C6-C20 aryl group is shown. )
A tubular nano-sized self-assembled body in which hexaperihexabenzocoronene (HBC) derivatives substituted with a fluorine-containing group represented by the formula are oriented in the plane direction.