JP2011068635A - Composite comprising liquid porphyrin derivative and nanocarbon material, manufacturing method of the same, charge-transporting material and electronic article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel nanomaterial. <P>SOLUTION: The composite includes a liquid porphyrin derivative represented by general formula (1) and a nanocarbon material. In the formula, R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each a hydrogen atom or an alkoxy group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composite comprising a porphyrin derivative that is liquid at low temperature and a nanocarbon material, a method for producing the same, a charge transporting material using the composite, and an electronic article using the charge transporting material It is.

  Porphyrin is a macrocyclic compound and its derivatives in which four pyrrol rings are alternately bonded to four methine groups at the α position, and there are a plurality of strong peaks in the visible region, and the Q band ( Qband), a compound having a characteristic peak called a soret band in the vicinity of 400 nm. Such porphyrins can coordinate with a metal at the center and have a large π-electron conjugated system, so that they can be used as electron carriers and have sharp absorption peaks in a specific wavelength region. Attempts have been made to apply to various uses such as electronic materials, optical materials, medical materials and display materials.

  Thus, porphyrin is expected to be applied to a wide range of industrial fields as a functional material in the future. However, there is a problem that the rigid skeleton easily aggregates and the solvent solubility is poor. For example, tetraphenylporphyrin (hereinafter sometimes abbreviated as “TPP”) is useful as a phosphorescent guest molecule in an organic EL device, but has a very low solvent solubility, and therefore forms a film in an organic EL device. However, it had to be formed by a vapor phase film forming method such as vacuum deposition.

  As an application of a porphyrin derivative, Patent Document 1 discloses a field effect transistor using an organic semiconductor layer containing an organic semiconductor made of a porphyrin compound having a specific structure. The porphyrin compound disclosed here has solvent solubility and forms a film by a wet film-forming method, but has a special structure in which a bicyclo compound is bonded to a pyrrole ring.

However, even if it has solvent solubility, it has been difficult to produce a high-concentration porphyrin derivative solution in which the primary particles are completely dispersed even in the solvent. On the other hand, the present inventors newly produced porphyrin derivatives that are liquid at low temperatures (Japanese Patent Application Nos. 2008-194463 and 2008-289655).
On the other hand, liquid fullerenes (Non-patent Document 1) and ionic liquids are attracting attention at the creation of nanomaterials at room temperature. For example, a bucky gel obtained by mixing an ionic liquid and fullerene is known (Non-Patent Document 2).

JP 2006-245559 A

J.AM.CHEM.SOC., 2006, 128, p.10384-10385 Science, 2003, 300, p.2072-2074

If a porphyrin derivative that is liquid at room temperature is obtained, a high-density porphyrin derivative that is completely uniformly dispersed can be obtained. Since liquid porphyrin derivatives have electron donor properties, it is thought that they can create new nanomaterials by interacting with fullerenes (C ₆₀ ), carbon nanotubes, etc. that have nonlinear optical properties and strong electron acceptor properties. It was.
An object of the present invention is to provide a composite composed of a porphyrin derivative and a nanocarbon material that are liquid at a low temperature, a charge transporting material using the composite, and an electronic article using the charge transporting material. is there.

  The present invention provides a composite composed of a porphyrin derivative that is liquid at 40 ° C. or less represented by the following general formula (1) and a nanocarbon material.

(In Formula (1), M represents an atom or compound that can be covalently or coordinated to 2H (hydrogen atom) or tetraphenylporphyrin. R ¹ , R ² , and R ³ are each independently hydrogen. An atom or a substituted or unsubstituted alkoxy group, R ^{1 s} , R ^{2 s} , and R ^{3 s} are the same, and R ² and R ³ are substituted or non-substituted having 7 to 15 carbon atoms. R ¹ is a hydrogen atom in a substituted alkoxy group, R ¹ and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms, R ² is a hydrogen atom, or R ¹ and R ² are carbon A substituted or unsubstituted alkoxy group of 7 to 15 and R ³ is a hydrogen atom, R ¹ , R ² and R ³ are a substituted or unsubstituted alkoxy group of 7 to 15 carbon atoms, or R ² has 8 carbon atoms R ¹ and R ³ are hydrogen atoms in a substituted or unsubstituted alkoxy group of -18.

  In the composite, the nanocarbon material is preferably at least one selected from the group consisting of fullerene and derivatives thereof, carbon nanotubes and derivatives thereof, and graphene and derivatives thereof.

  The composite according to the present invention has a Bragg angle (2θ) of 3.6 ° ± 0.2 °, 6.2 ° ± 0.2 °, and 7.2 ° in the X-ray diffraction spectrum by CuKα ray. Examples include a complex showing a diffraction peak in at least one selected from the group consisting of ± 0.2 °.

  Moreover, this invention is represented by the said General formula (1) which has the process of carrying out at least pressurization mixing of the porphyrin derivative which is liquid at 40 degrees C or less represented by the said General formula (1), and a nanocarbon material. There is also provided a method for producing a composite comprising a porphyrin derivative that is liquid at 40 ° C. or lower and a nanocarbon material.

The present invention also provides a charge transport material comprising the composite according to the present invention.
Furthermore, the present invention provides an electronic article comprising the charge transport material according to the present invention.

  The present invention relates to a novel nanomaterial, a composite comprising a porphyrin derivative that is liquid at low temperature and a nanocarbon material, a method for producing the composite, a charge transporting material using the composite, and the charge transporting material There is an effect that an electronic article using can be provided.

Figure 1 shows the absorption spectrum of the mixture and PMMA of PMMA and _{C 60.} FIG. 2 shows the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10), and 100% of the liquid porphyrin derivative. It shows the absorption spectrum normalized 430nm thin film as a reference, a mixture of PMMA and _{C 60} an absorption spectrum of a thin film of (1 wt%). FIG. 3 shows the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10), and 100% of the liquid porphyrin derivative. The absorption spectrum normalized with respect to 655 nm of the thin film is shown. FIG. 4 shows the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10), and 100% of the liquid porphyrin derivative. The emission spectrum normalized with respect to 660 nm of the thin film is shown. FIG. 5 shows the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10), and 100% of the liquid porphyrin derivative. The emission spectrum normalized with respect to 730 nm of the thin film is shown. FIG. 6 shows the DSC measurement result of Example 5. FIG. 7 shows the DSC measurement result of Example 6. FIG. 8 shows the DSC measurement result of Example 7. FIG. 9 shows the DSC measurement result of Example 8. FIG. 10 shows the DSC measurement result of Example 9. FIG. 11 shows the DSC measurement result of Example 10. FIG. 12 shows the result of enlarging the vicinity of −10 ° C. of the second scan of the DSC measurement of the composites of Examples 5 to 10 (C ₆₀ content: 1, 2, 5, 10, 15, 20 wt%). FIG. 13 shows the result of enlarging the vicinity of 100 ° C. of the second scan of DSC measurement of the composites of Examples 5 to 10 (C ₆₀ content: 1, 2, 5, 10, 15, 20 wt%). FIG. 14 shows the first temperature rise measurement result of the X-ray diffraction measurement of the composite of Example 8 (C ₆₀ content: 10 wt%). FIG. 15 shows the second temperature rise measurement result of the X-ray diffraction measurement of the composite of Example 8 (C ₆₀ content: 10 wt%). FIG. 16 shows the X-ray diffraction measurement results of the porphyrin derivative alone. Figure 17 _shows the X-ray diffraction measurement results of _{C 60} alone. FIG. 18 shows an enlarged portion of the second temperature rise measurement result of the X-ray diffraction measurement of the composite of Example 9 (C ₆₀ content: 15 wt%).

  The composite according to the present invention is a composite composed of a porphyrin derivative that is liquid at 40 ° C. or less and represented by the following formula (1), and a nanocarbon material.

(In Formula (1), M represents an atom or compound that can be covalently or coordinated to 2H (hydrogen atom) or tetraphenylporphyrin. R ¹ , R ² , and R ³ are each independently hydrogen. An atom or a substituted or unsubstituted alkoxy group, R ^{1 s} , R ^{2 s} , and R ^{3 s} are the same, and R ² and R ³ are substituted or non-substituted having 7 to 15 carbon atoms. R ¹ is a hydrogen atom in a substituted alkoxy group, R ¹ and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms, R ² is a hydrogen atom, or R ¹ and R ² are carbon A substituted or unsubstituted alkoxy group of 7 to 15 and R ³ is a hydrogen atom, R ¹ , R ² and R ³ are a substituted or unsubstituted alkoxy group of 7 to 15 carbon atoms, or R ² has 8 carbon atoms R ¹ and R ³ are hydrogen atoms in a substituted or unsubstituted alkoxy group of -18.

Conventionally, porphyrin derivatives have extremely low solvent solubility, whereas porphyrin derivatives used in the present invention have liquidity at a low temperature of 40 ° C. or lower and have high thermal stability. Such a liquid porphyrin derivative is a high-density porphyrin derivative that has properties unique to porphyrin and is completely uniformly dispersed with a pure substance. When such a liquid porphyrin derivative is used as an electron donor-type dispersion medium and a nanocarbon material such as fullerene (C ₆₀ ) or carbon nanotube having strong electron acceptor properties is dispersed as a dispersoid, both of them are in a high density state. It was revealed that a complex of liquid porphyrin derivative and nanocarbon material was formed. Such a complex can express a specific function as, for example, a charge transport material, a photoelectric conversion material, or an organic semiconductor material.

  Since the porphyrin derivative used in the complex of the present invention has an alkoxy group having 2 to 5 specific carbon atoms at a specific position of the benzene ring as represented by the above formula (1), it is a conventional porphyrin derivative. Then, it has a unique property of being liquid at 40 ° C. or lower, which could not be achieved. Here, the liquid state at 40 ° C. or lower refers to a case where it has fluidity at 40 ° C. or lower, and includes a so-called paste form. Even if it is obtained as a solid at 40 ° C. or lower at the time of synthesis, it includes a case where it has fluidity at any temperature of 40 ° C. or lower after melting once by heating. Even a compound obtained as a solid at 40 ° C. is subjected to differential scanning calorimetry (DSC), solidified after being melted once in the first temperature rise and cooling, and then specific to the substance by the second temperature rise and cooling. When the melting point is measured, when the melting point is less than 40 ° C., it is included in the case of having fluidity at 40 ° C. or less.

The porphyrin derivative used in the present invention was molecularly designed for the purpose of making it a liquid with a pure substance, not a liquid with a mixture. Therefore, in order to facilitate the purification to obtain a pure substance, it has a symmetric molecular structure.
Therefore, the alkoxy group is located at the 3,5 position, 2,4,6 position, 3,4,5 position, 2,3,5,6 position, or 2,3,4,5,6 position of the benzene ring. Substituted, alkoxy groups are identical at the 2nd and 6th positions and the 3rd and 5th positions. Moreover, the substitution position and kind of the alkoxy group of four benzene rings which exist in Formula (1) are the same. That is, the porphyrin derivative that is liquid at 40 ° C. or lower according to the present invention is the formula (1), wherein R ² and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms and R ¹ is a hydrogen atom. , R ¹ and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms and R ² is a hydrogen atom, or R ¹ and R ² are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms R ³ is a hydrogen atom, R ¹ , R ² and R ³ are a substituted or unsubstituted alkoxy group having 7 to 15 carbon atoms, or R ² is a substituted or unsubstituted group having 8 to 18 carbon atoms. In the alkoxy group, R ¹ and R ³ are hydrogen atoms.

In the liquid porphyrin derivative according to the present invention, among others, R ² and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms and R ¹ is a hydrogen atom, or R ² is 8 to 8 carbon atoms. In the 18 substituted or unsubstituted alkoxy groups, R ¹ and R ³ are preferably hydrogen atoms. In this case, because the structure of the alkyl chain extends in a direction that does not overlap the surface of the porphyrin ring in the molecule, the spatial distance between the porphyrin rings between the porphyrin derivative molecules tends to be small, and the functionality such as electron transfer is improved. There is expected.

  As shown in the production examples and comparative production examples to be described later, even if the number of carbon atoms of the substituted alkoxy group is too small or too large, the melting point rises and there is a tendency that a liquid state cannot be achieved at 40 ° C. or lower. Therefore, the number of carbon atoms of the alkoxy group in the porphyrin derivative that is liquid at 40 ° C. or lower of the present invention is 7 to 15 when the alkoxy group is trisubstituted on the benzene ring, and 8 to 18 when the alkoxy group is disubstituted. .

The substituted alkoxy group is a substituted or unsubstituted alkoxy group. That is, when an alkoxy group is described as —OR, the R is a substituted or unsubstituted alkyl group having 7 to 15 carbon atoms or 8 to 18 carbon atoms. The alkyl group may contain a cyclic structure in addition to a linear or branched chain.
Examples of the unsubstituted alkyl group having 7 to 18 carbon atoms include n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, and n-tridecyl. And linear alkyl groups such as a group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Moreover, the branched alkyl group by which one or more hydrogen atoms other than the terminal of these linear alkyl groups was substituted by alkyl groups, such as a methyl group, an ethyl group, n-propyl group, an isopropyl group, can be mentioned. The branched alkyl group is preferably a branched alkyl group in which one or more hydrogen atoms are substituted with a methyl group or an ethyl group on the linear alkyl group. In the case of a branched alkyl group, for example, it is also preferable to use a branched structure having an object. Moreover, the alkyl group containing cyclic structures, such as cyclohexyl, may be sufficient.

  Furthermore, examples of the alkyl group having 7 to 18 carbon atoms having a substituent include those in which one or more hydrogen atoms of the alkyl group exemplified above are substituted with a substituent that does not inhibit the effect of the present invention. it can. For example, one or more hydrogen atoms of an alkyl group are substituted with halogen atoms, substituted or unsubstituted aromatic groups, trifluoromethyl groups, cyano groups, nitro groups, alkoxy groups, aryloxy groups, alkylthio groups, dialkylamino groups, etc. Can be exemplified.

In the liquid porphyrin derivative represented by the above formula (1) according to the present invention, R ^{1 s} , R ^{2 s} , and R ^{3 s} are the same, but R ¹ , R ² , and R ³ have a plurality. In this case, the plurality of alkoxy groups may be the same as or different from each other. From the viewpoint of the synthesis of the porphyrin derivative, it is preferable that the plurality of alkoxy groups are all the same.

By appropriately selecting the alkoxy group, the number of substitutions, and the substitution position, various properties such as the viscosity of the porphyrin derivative used in the present invention and the thermal properties such as the thermal decomposition temperature can be adjusted. Depending on the type of the substituent, since the melting point and freezing point are less than 0 ° C., some of them have a liquid state over a wide range from less than 0 ° C. to the thermal decomposition temperature. Further, depending on the type of alkoxy and the substitution position, the thermal decomposition temperature is higher than that of conventional tetraphenylporphyrin, and the thermal stability is increased. For this reason, the alkoxy group, the number of substitutions, and the substitution position can be appropriately selected depending on the field to which the complex of the present invention is applied.
For example, when the alkoxy group is bonded to the 3,4,5-position, that is, when R ² and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms and R ¹ is a hydrogen atom, the melting point is 0 ° C. Therefore, it can be stably used as a liquid even at a low temperature.

In Formula (1), M represents an atom or compound that can be covalently or coordinately bonded to 2H (hydrogen atom) or tetraphenylporphyrin. When M is 2H, it has a structure in which hydrogen atoms are bonded to two nitrogen atoms. The atom or compound capable of covalent bond or coordinate bond with tetraphenylporphyrin is appropriately selected from the viewpoint of controlling functionality. Examples of atoms or compounds that can be covalently or coordinated with tetraphenylporphyrin include, for example, Ti, Co, Ni, Cu, Al, V, In, Cr, Ga, Ge, Mg, Pt, Pd, Fe, Zn, etc. Or metal oxides thereof, or oxides or fluorides thereof, halides such as chlorides, bromides and iodides, hydroxides and the like. Specific examples include Ti = O, AlCl, V = O, InCl, GaCl, and GaOH.
As shown in Japanese Patent Application No. 2007-207987 by the present inventor, in the porphyrin derivative, the thermophysical properties such as the melting point are less affected by the type of atoms or compounds in the porphyrin ring, and greatly affected by the type of substituent. .

  The liquid porphyrin derivative used in the present invention can be produced according to the method for producing a liquid porphyrin derivative described in Japanese Patent Application No. 2008-194463 and Japanese Patent Application No. 2008-289655 by the present inventor.

  On the other hand, the nanocarbon material used in the present invention refers to a carbon material having at least one dimension on the order of nanometers. Examples of the nanocarbon material include one or more selected from the group consisting of fullerene and derivatives thereof, carbon nanotubes and derivatives thereof, and graphene and derivatives thereof.

  Fullerene refers to a group of spherical shell-like carbon molecules including C60. As the fullerene, a fullerene having 60 or more carbon atoms can be used, and examples thereof include C60, C70, C76, C78, C80, C82, C84, C86, C90, C92, C94, C96, and C124. The fullerene derivative refers to a compound or composition in which an atomic group forming a part of an organic compound or an atomic group composed of an inorganic element is bonded to or included in at least one carbon constituting the fullerene. The fullerene derivatives include [6,6] -phenyl C61-butyric acid methyl ester ([60] PCBM), [6,6] -phenyl C61-butyric acid n-butyl ester ([60] PCNBB), [6,6]. -Phenyl C61-butyric acid i-butyl ester ([60] PCBIB), [6,6] -phenyl C71-butyric acid methyl ester ([70] PCBM), fullerene hydroxide, hydrogenated fullerene, fullerene represented by the following formula, And metal-encapsulated fullerenes are also included.

  A carbon nanotube refers to a substance in which a six-membered ring network (graphene sheet) made of carbon has a single-layer or multilayer coaxial tube. The carbon nanotube has a diameter of 2 to 50 nm and a length of about 1 to 10 μm. The carbon nanotube derivative is a compound or composition in which an atomic group forming a part of an organic compound or an atomic group composed of an inorganic element is bonded to or included in at least one carbon constituting the carbon nanotube.

Strictly speaking, graphene refers to a sheet of sp ² -bonded carbon atoms having a thickness of 1 atom, but in the present invention, several layers of graphene, which is ultrathin graphite up to about 10 layers, are also included. In the present invention, nanographene having a nanoscale size is used. A graphene derivative refers to a compound or composition in which an atomic group forming a part of an organic compound or an atomic group composed of an inorganic element is bonded to or included in at least one carbon constituting graphene.

  The method for producing a composite comprising a liquid porphyrin derivative and a nanocarbon material represented by the above formula (1) of the present invention at 40 ° C. or lower is not particularly limited as long as the composite can be obtained. By mixing a porphyrin derivative that is liquid at 40 ° C. or less represented by the formula (1) and the nanocarbon material, the composite can be obtained.

  Specifically, the composite of the present invention may be obtained by mixing only a porphyrin derivative and a nanocarbon material that are liquid at 40 ° C. or less represented by the above formula (1). Alternatively, the composite of the present invention is prepared by dissolving or dispersing a liquid porphyrin derivative and a nanocarbon material in a solvent such as toluene at 40 ° C. or less represented by the above formula (1), and then mixing the solvent. You may obtain by removing.

When no solvent is used, the composite of the present invention can be produced by mixing at least a pressurized porphyrin derivative and a nanocarbon material represented by the above formula (1) at 40 ° C. or lower. From the viewpoint of improving the yield of the body. As the degree of pressure in the case of pressure mixing, for example, in a laboratory scale, it is preferable to apply pressure enough to mix while grinding in a mortar. Specifically, when using a mixing device such as a homogenizer or a mill, for example, 1 It is preferable to mix while rotating at a rotational speed of ˜1000 rpm, more preferably 10˜100 rpm. Further, it is preferable to apply a pressure of about 0.1 to 1.0 MPa, more preferably about 0.2 to 0.9 MPa.
Furthermore, heating at the time of pressure mixing or after pressure mixing is preferable from the viewpoint of improving the yield of the composite. The heating temperature is preferably appropriately selected from 100 to 150 ° C. from the viewpoint of annealing.

  As a preferred embodiment of the composite comprising a porphyrin derivative and a nanocarbon material which are obtained at 40 ° C. or less and represented by the above formula (1) according to the present invention, the X-ray by CuKα ray is obtained. In the diffraction spectrum, at least one selected from the group consisting of 3.6 ° ± 0.2 °, 6.2 ° ± 0.2 °, and 7.2 ° ± 0.2 ° of the Bragg angle (2θ) A composite showing a diffraction peak at 3.6 ° ± 0.2 °, a 6.2 ° ± 0.2 °, and a 7.2 ° ± 0.2 ° Bragg angle (2θ). The body is mentioned. Examples of the complex exhibiting the diffraction peak include a complex composed of the porphyrin derivative and fullerene. The measurement conditions of the X-ray diffraction spectrum using CuKα rays are, for example, a tube X-ray diffractometer (manufactured by Rigaku, SmartLab), for example, tube voltage: 45 kV, tube current: 200 mA, optical system: parallel beam optical system, monochromatization : Multilayer mirror, sampling interval: 0.02 deg, scanning angle: 2 to 40 deg, scanning speed: 4 deg / min, heating rate: 10 ° C./min, holding time 5 minutes.

In the X-ray diffraction spectrum, the vertical axis represents the diffraction intensity and the horizontal axis represents the Bragg angle (2θ), but the 2θ value is observed within a certain range even when the same crystal form is measured. Is done. Specifically, ± 0.2 ° is a general variation degree, but a larger error may occur depending on measurement conditions. When comparing the crystal forms of the composites based on 2θ values, those skilled in the art compare the crystal forms of the composites in consideration of these variations.
In addition, since the Bragg angle is changed depending on the substituent of the porphyrin derivative in the complex of the present invention, the metal contained, and the like, the complex of the present invention is not limited to the complex exhibiting the Bragg angle.

  Since the composite composed of the porphyrin derivative and the nanocarbon material that is liquid at 40 ° C. or less and represented by the above formula (1) according to the present invention obtained as described above has a large π-electron conjugated system, the charge carrier And can be widely applied to the electronics field. By utilizing the high charge transportability, for example, it can be used as a charge transport material, an organic semiconductor material, or a photoelectric conversion material. In addition, by selecting a metal, it is possible to adjust its electrical characteristics and optical characteristics.

The charge transporting material according to the present invention is composed of a composite composed of a porphyrin derivative and a nanocarbon material that are liquid at 40 ° C. or lower and represented by the above formula (1) according to the present invention.
The charge transport material according to the present invention can also be used as a so-called photoelectric conversion material, organic semiconductor material, or the like. The charge transporting material according to the present invention can be suitably used for an electronic article including the charge transporting material.

  The electronic article according to the present invention includes the charge transporting material according to the present invention. In the electronic article according to the present invention, if the charge transporting material according to the present invention is included in any of the configurations including the charge transporting material, the other configurations can be the same as those conventionally known. . As an electronic article which concerns on this invention, a solar cell, a photoelectric conversion element (photodiode), a field effect transistor etc. can be mentioned, for example.

In the following production examples, all reagents were obtained using commercially available products. The pyrrole was distilled under reduced pressure and stored under an argon atmosphere. Other reagents were used in the reaction without purification. Silica gel 60 manufactured by Merck was used as silica gel column chromatography during purification.
Moreover, the structure of all the obtained compounds was confirmed by NMR measurement and MALDI-TOF-MS measurement. ^{For 1} HNMR and ¹³ CNMR measurements, JNM-LA400WB (manufactured by JEOL; 400 MHz) was used, and for MALDI-TOF-MS measurement, REFLEX II (manufactured by BRUKER) or AXIMA-CFR plus (manufactured by Shimadzu Corporation) was used.

(Production Example 1)
According to the following scheme, a liquid porphyrin derivative represented by the above formula (1) (5,10,15,20-tetrakis [3,4,5-tris (heptyloxy) phenyl] porphyrin) was produced. Note that direct reduction with LiAlH ₄ from ethyl 3,4,5-tris (heptyloxy) benzoate to 3,4,5-tris (heptyloxy) benzyl alcohol is a by-product (perhaps only the carbonyl group of the ester is reduced). In addition, there was a tendency for the yield to decrease due to the production or decomposition of 1-ethyl-3,4,5-tris (heptyloxy) benzene. Therefore, after the ester was hydrolyzed and converted to a carboxylic acid, a two-step reaction in which LiAlH _{4 was} reduced was examined. As a result, a better yield than direct reduction was given in two steps.

In the formula, R is an alkyl group.
i) alkyl bromide, K ₂ CO ₃ , DMF, 90 degree. ii) KOH, THF-Methanol-water, reflux. iii) LiAlH ₄ , THF, reflux. iv) MnO ₂ , CHCl ₃ , room temperature

In the formula, R is an alkyl group.
v) TFA, CHCl ₃ , room temperature, then DDQ following NEt ₃ .

(1) Synthesis of ethyl 3,4,5-tris (heptyloxy) benzoate
Ethyl 3,4,5-trihydroxybenzoate (5.011 g, 25.286 mmol) and potassium carbonate (12.229 g, 88.484 mmol) in DMF 40 ml in the presence of 1-bromoheptane (16.0 ml, 0.102 mol) in an argon atmosphere 90 Stir at ~ 100 degrees. After extracting the reaction product into the organic layer with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, and dried over anhydrous magnesium sulfate. The residue obtained by concentration after filtration is purified by silica gel column chromatography (developing solvent: hexane → chloroform) to give the desired product (ethyl 3,4,5-tris (heptyloxy) benzoate, formula [A Of OR was heptyloxy) (oil, 9.006 g, yield 72.3%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.87−0.91 (m, 9H, CH ₃ ), 1.30−1.40 (m, 21H, CH ₃ + CH ₂ ), 1.44−1.51 (m, _{6H, CH 2), 1.71-1.85 (} m, 6H, CH 2), 4.00-4.03 (m, 6H, ArOCH 2), 4.355 (q, J = 7.1 Hz, 2H, CH 3 CH 2 O), 7.255 ( s, 2H, arom.H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.075, 14.09, 14.39, 22.60, 22.65, 25.98, 26.02, 29.04, 29.20, 29.29, 30.30, 31.80, 31.89 (aliphatic), 60.95, 69.13, 73.46 ( ether), 107.92, 125.01, 142.25, 152.77 (aromatic), 166.47 (carbonyl).

(2) Synthesis of 3,4,5-tris (heptyloxy) benzoic acid
Ethyl 3,4,5-trisheptyloxybenzoate (8.291 g, 16.826 mmol) and potassium hydroxide (1.588 g, 28.304 mmol) in THF-methanol-water (100 ml-25 ml-5 ml) under argon The mixture was heated to reflux for several hours in the atmosphere. The reaction mixture was cooled, water was added, and the mixture was hydrolyzed by adding hydrochloric acid under ice cooling, and the pH was further adjusted to about 1. After concentrating the solution, the reaction product was extracted into the organic layer with chloroform-water, and then the organic layer was washed once with water, dried over anhydrous magnesium sulfate, filtered and concentrated to freeze the residue. By drying, the target compound (ethyl 3,4,5-tris (heptyloxy) benzoate, OR of formula [B] was heptyloxy) (solid, 7.634 g, yield 97.6%) was obtained.

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.87−0.91 (m, 9H, CH ₃ ), 1.29−1.52 (m, 24H, CH ₂ ), 1.72−1.86 (m, 6H, CH ₂ ), 4.01−4.06 (m, 6H, ArOCH ₂ ), 7.32 (s, 2H, arom.H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.09, 14.10, 22.61, 22.66, 25.96, 26.01, 29.04, 29.20, 29.25, 30.31, 31.80, 31.895 (aliphatic), 69.14, 73.54 (ether), 108.465 , 123.55, 143.07, 152.825 (aromatic), 171.50 (carbonyl)

(3) Synthesis of 3,4,5-tris (heptyloxy) benzyl alcohol
Hydrogen was generated by adding THF (40 ml) to a mixture of 3,4,5-bis (heptyloxy) benzoic acid (7.618 g, 16.394 mmol) and LiAlH ₄ (0.754 g, 19.866 mmol) under ice-cooling in an argon atmosphere. Refluxed overnight after it had settled. After cooling to room temperature, the mixture was stirred under ice-cooling, ethyl acetate was added, the remaining LiAlH ₄ was deactivated, and then a small amount of water was added and further stirred. Chloroform was added and stirred at room temperature, and anhydrous magnesium sulfate was added and stirred for several tens of minutes. The filtrate obtained by filtering this solution was concentrated, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform → chloroform-methanol (98: 2 v / v)) to obtain the target. Compound (3,4,5-tris (heptyloxy) benzyl alcohol, OR of formula [C] was heptyloxy) (solid, 6.137 g, yield 83.1%) was obtained.

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.87−0.905 (m, 9H, CH ₃ ), 1.25−1.50 (m, 24H, CH ₂ ), 1.655 (t, J = 6.0 Hz, 1H, OH), 1.70-1.83 (m, 6H, CH ₂ ), 3.92-3.985 (m, 6H, ArOCH ₂ ), 4.59 (d, J = 5.6 Hz, 2H, ArCH ₂ OH), 6.56 (s, 2H , arom.H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.075, 14.095, 22.61, 22.66, 26.03, 26.06, 29.06, 29.25, 29.40, 30.31, 31.82, 31.915 (aliphatic), 65.67, 69.08, 73.42 (ether) , 105.32, 136.00, 137.58, 153.265 (aromatic).

(4) Synthesis of 3,4,5-tris (heptyloxy) benzaldehyde
Mixture of 3,4,5-trisheptyloxybenzyl alcohol (6.123 g, 13.585 mmol) and manganese (IV) oxide (4.732 g, 54.430 mmol) in chloroform in the presence of anhydrous magnesium sulfate under argon atmosphere at room temperature. And stirred for several days. The residue obtained by concentrating the filtrate after filtration is separated and purified by silica gel column chromatography (developing solvent: chloroform) to give the desired compound (3,4,5-tris (heptyloxy) benzaldehyde, formula [D]. Of OR was heptyloxy) (oil, 4.390 g, yield 72.0%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.87−0.91 (m, 9H, CH ₃ ), 1.28−1.40 (m, 18H, CH ₂ ), 1.43−1.51 (m, 6H, CH ₂ ), 1.72-1.87 (m, 6H, CH ₂ ), 4.02−4.07 (m, 6H, ArOCH ₂ ), 7.08 (s, 2H, arom.H), 9.83 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.08, 14.10, 22.60, 22.65, 25.95, 26.00, 29.02, 29.18, 29.22, 30.315, 31.79, 31.88 (aliphatic), 69.18, 73.61 (ether), 107.76 , 131.40, 143.755, 153.48 (aromatic), 191.34 (aldehyde).

(5) Synthesis of 5,10,15,20-tetrakis [3,4,5-tris (heptyloxy) phenyl] porphyrin Pyrrole (0.40 ml) and 3,4,5-tris (heptyloxy) benzaldehyde (2.077 g, 4.629 mmol) was stirred in chloroform (450 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (TFA) (0.5 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) (1.082 g, 4.766 mmol), and the mixture was further stirred for 5 hours. The solution was concentrated after hydrolysis by adding triethylamine (1.0 ml), and the resulting residue was passed through silica gel using chloroform as a developing solvent (performed several times to remove the black component as much as possible). At this stage, the target product and the starting benzaldehyde derivative are mixed in a molar ratio of about 4: 1 (according to the integral ratio of NMR). Therefore, in order to remove unreacted raw materials, this mixture and sodium borohydride (NaBF ₄ ) (0.207 g, 5.472 mmol) were added in THF-ethanol (15 ml-15 ml (1: 1 v / v)). After stirring overnight at room temperature under argon, the solvent was distilled off, and the reaction product was extracted into the organic layer with chloroform-water. The organic layer is washed twice with water, dried over anhydrous sodium sulfate, filtered and concentrated, and the resulting residue is purified by silica gel column chromatography (developing solvent: chloroform) and lyophilized to give the desired compound (5,10,15,20-tetrakis [3,4,5-tris (heptyloxy) phenyl] porphyrin, OR of formula [E] is heptyloxy) (red purple oil, 0.291 g, 12.7% yield) Obtained.

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.81 (s, 2H, NH), 0.845 (t, J = 6.8 Hz, 24H, CH ₃ ), 0.96 (t, J = 6.8 Hz , 12H, CH ₃ ), 1.23−1.52 (m, 88H, CH ₂ ), 1.62−1.70 (m, 8H, CH ₂ ), 1.83−1.90 (m, 16H, CH ₂ ), 1.94−2.01 (m, 8H , CH ₂ ), 4.08 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 4.29 (t, J = 6.6 Hz, 8H, ArOCH ₂ ), 7.415 (s, 8H, arom.H), 8.94 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1985.30 (M ⁺ ).

Purification of a porphyrin derivative having liquidity is difficult to recrystallize because it is liquid, and purification is difficult because the _Rf values of the raw material aldehyde and the target compound porphyrin derivative are almost equal. Although separation and purification by preparative GPC was taken into account, in general, substances such as phthalocyanine derivatives may be adsorbed on the column. Thus, focusing on the substituents of the raw material, separation and purification became possible by converting the aldehyde into a benzyl alcohol derivative.

(Production Example 2)
According to the same scheme as in Production Example 1, except that 1-bromooctane was used in place of 1-bromoheptane in Production Example 1, the desired product 5,10,15,20-tetrakis [3, 4,5-tris (octyloxy) phenyl] porphyrin (OR of formula [E] is octyloxy) (purple oily substance, 0.256 g, yield 11.4%) was obtained.

(Production Example 3)
In Production Example 1, 5,10,15,20-tetrakis [3,4,5-5-tetrakis [3,4,5-] was prepared according to the same scheme as in Production Example 1 except that 1-bromononane was used instead of 1-bromoheptane. Tris (nonyloxy) phenyl] porphyrin (OR of formula [E] is nonyloxy) (red purple oily substance, 0.295 g, yield 10.8%) was obtained.

(Production Example 4)
In Production Example 1, 5,10,15,20-tetrakis [3,4,5-5-tetrakis [3,4,5-] was prepared according to the same scheme as in Production Example 1 except that 1-bromodecane was used instead of 1-bromoheptane. Tris (decyloxy) phenyl] porphyrin (OR of formula [E] was decyloxy) (red purple oily substance, 0.264 g, yield 9.7%) was obtained.

(Production Example 5)
In Production Example 1, 5,10,15,20-tetrakis [3,4,5] according to the same scheme as in Production Example 1 except that 1-bromoundecane was used instead of 1-bromoheptane. -Tris (undecyloxy) phenyl] porphyrin (OR of formula [E] was undecyloxy) (red purple oily substance, 0.316 g, yield 11.4%) was obtained.

(Production Example 6)
In Production Example 1, 5,10,15,20-tetrakis [3,4,5] was used according to the same scheme as in Production Example 1, except that 1-bromododecane was used instead of 1-bromoheptane. -Tris (dodecyloxy) phenyl] porphyrin (OR of formula [E] is dodecyloxy) (red purple oily substance, 0.258 g, yield 9.6%) was obtained.

(Production Example 7)
In Production Example 1, 5,10,15,20-tetrakis [3,4,4] was used according to the same scheme as in Production Example 1, except that 1-bromotridecane was used instead of 1-bromoheptane. 5-Tris (tridecyloxy) phenyl] porphyrin (OR in formula [E] is tridecyloxy) (red purple oily substance, 0.388 g, yield 14.0%) was obtained.

(Production Example 8)
In Production Example 1, 5,10,15,20-tetrakis [3,4,5] according to the same scheme as in Production Example 1 except that 1-bromotetradecane was used instead of 1-bromoheptane. -Tris (tetradecyloxy) phenyl] porphyrin (OR of formula [E] is tetradecyloxy) (red purple oily substance, 0.450 g, yield 12.0%) was obtained.

(Comparative Production Example 1)
5,10,15,20-tetrakis [3] in the same manner as in Production Example 1 except that the formula [C] was synthesized from the formula [A] without passing through the formula “B” as in the following scheme. , 4,5-tris (pentyloxy) phenyl] porphyrin (OR of formula [E] is pentyloxy) (reddish purple solid, 0.307 g, yield 13.5%).

In the formula, R is an alkyl group.
i) alkyl bromide, K ₂ CO ₃ , DMF, 90 degree.vi) LiAlH ₄ , THF, reflux.

(Comparative Production Example 2)
As in Comparative Production Example 1, 5,10,15,20-tetrakis [3,4,5-tris (hexyloxy) phenyl] porphyrin (OR in formula [E] is hexyloxy) (red purple oily substance, 0.241 g, yield 10.4%). Although it was an oily substance immediately after preparation, it partially solidified after several months.

(Production Example 9)
Similar to Comparative Production Example 1, the formula [C] was synthesized from the formula [A] without going through the formula “B”, and 5,10,15,20-tetrakis [3,4,5-tris (penta Decyloxy) phenyl] porphyrin (OR of formula [E] is pentadecyloxy) (red purple solid, 0.186 g, yield 4.7%) was obtained. Since there was a difference in polarity between the unreacted raw material and the target product, a step of purifying the benzaldehyde derivative after conversion into a benzyl alcohol derivative was not necessary.

The following thermophysical properties of the porphyrin derivative obtained above were evaluated.
Simultaneous differential heat / thermogravimetric measurement (TG-DTA) is performed at a temperature increase rate of 10 K / min in a nitrogen atmosphere using a TG / DTA simultaneous measurement device (product name: DTG-60A, manufactured by Shimadzu Corporation). The temperature was measured from 30 ° C. to 600 ° C., and the weight loss temperature of 2% was defined as the thermal decomposition temperature. Differential scanning calorimetry (DSC) is measured using a differential scanning calorimeter (product name: DSC-60, manufactured by Shimadzu Corporation) at a heating / cooling rate of 10 K / min in a nitrogen atmosphere. The melting point (Tm) and the freezing point (Tf) were measured from -100 ° C to 100 ° C. About melting | fusing point (Tm) and freezing point (Tf), temperature rising and cooling were performed twice, respectively. Table 1 shows the results.

From the results in Table 1, it was suggested that the thermophysical properties depend on the type of substituent. It was revealed that Production Examples 4 to 6 in which three alkoxy groups having a linear alkyl group having 10 to 12 carbon atoms were substituted were liquid even at temperatures lower than 0 ° C. In Production Examples 1 to 3 having linear alkyl having 7 to 9 carbon atoms, no peak of melting point due to DTA is observed in the range from 30 ° C. to 600 ° C. as measured by TG-DTA, and DSC-60 No melting point or freezing point was observed within the range from -100 ° C. to 100 ° C. from the measurement by. Production Examples 1 to 3 may have a melting point or a freezing point at −100 ° C. or lower.
In Production Example 9 in which the alkoxy group having 15 carbon atoms was substituted, the melting point (Tm) exceeded 25 ° C., and it became clear that the liquid state could not be achieved at 25 ° C. Had. In Production Example 9 in which an alkoxy group having 15 carbon atoms was substituted, the melting points obtained by the first scan and the second scan were different from those of other derivatives having an alkoxy group having 14 or less carbon atoms. However, the melting points in the second and third scans were within the measurement error range. In the solid state, the molecules are condensed, and the melting point is measured to be higher in the first scan. However, it is considered that the melting of the molecules is suppressed by melting once, and the inherent melting point is measured.
Comparative Production Example 2 in which an alkoxy group having 6 carbon atoms was substituted was an oily substance immediately after preparation, but partially solidified after several months, and a peak was observed at around 80 ° C. from DSC measurement. This is probably due to partial aggregation. In Comparative Production Example 2, there is a possibility that there are two phases of a solid state and a liquid state.

(Production Example 10)
According to the following scheme, a liquid porphyrin derivative represented by the above formula (1) (5,10,15,20-tetrakis [3,5-bis (alkoxy) phenyl] porphyrin) was produced.

In the formula, R is an alkyl group.
i) alkyl bromide, K ₂ CO ₃ , DMF, 90 degree; ii) MnO ₂ , CHCl ₃ room temperature

In the formula, R is an alkyl group.
iii) TFA, CHCl ₃ , room temperature, then DDQ following NEt ₃ .

(1) Synthesis of 3,5-bis (octyloxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (7.017 g, 50.072 mmol) and potassium carbonate (17.221 g, 0.125 mol) were added to 1-bromooctane (22.0) in 30 ml of dry DMF. ml, 0.126 mol) and stirred at 90 ° C. in an argon atmosphere. After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the resulting residue was subjected to silica gel column chromatography ( By purifying with a developing solvent: chloroform), 3,5-bis (octyloxy) benzyl alcohol (oil, 14.150 g, yield 77.5%) was obtained.

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.89 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.24−1.36 (m, 16H, CH ₂ ), 1.40−1.475 (m, 4H, CH ₂ ), 1.64 (t, J = 6.2 Hz, 1H, OH), 1.73−1.80 (m, 4H, CH ₂ ), 3.93 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 4.62 (d , J = 6.4 Hz, 2H, CH ₂ O), 6.38 (t, J = 2.2 Hz, 1H, arom.H), 6.50 (d, J = 2.4 Hz, 2H, arom.H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.08, 22.64, 26.04, 29.23, 29.25, 29.33, 31.80 (aliphatic), 65.48, 68.06 (ether), 100.55, 105.05, 143.17, 160.54 (aromatic).

(2) Synthesis of 3,5-bis (octyloxy) benzaldehyde A mixture of 3,5-bis (octyloxy) benzyl alcohol (7.159 g, 19.637 mmol) and manganese oxide (IV) (7.002 g, 80.541 mol) was dried in 45 ml. The mixture was stirred for several days at room temperature under an argon atmosphere in the presence of anhydrous magnesium sulfate. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform) to give 3,5-bis (octyloxy) benzaldehyde (oil, 4.720 g, yield 91.1%) Got.

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.89 (t, J = 6.8 Hz, 6H, CH ₃ ), 1.26−1.39 (m, 16H, CH ₂ ), 1.435−1.49 (m, 4H, CH ₂ ), 1.75−1.82 (m, 4H, CH ₂ ), 3.98 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 6.695 (t, J = 2.6 Hz, 1H, arom.H), 6.98 (d, J = 2.4 Hz, 2H, arom.H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.08, 22.64, 25.99, 29.12, 29.21, 29.30, 31.79 (aliphatic), 68.44 (ether), 107.59, 108.02, 138.30, 160.76 (aromatic), 192.10 ( aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (octyloxy) phenyl] porphyrin Mixture of pyrrole (0.40 ml) and 3,5-bis (octyloxy) benzaldehyde (1.997 g, 5.508 mmol) Was stirred in chloroform (450 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (TFA) (0.62 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) (1.991 g, 8.771 mmol), and the mixture was further stirred for 5 hours. Triethylamine (1.3 ml) was added and the solution was concentrated after hydrolysis, and the resulting residue was passed through silica gel using chloroform as a developing solvent. Subsequently, 5,10,15,20-tetrakis [3,5-bis (octyloxy) phenyl] porphyrin is purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)). (Red purple viscous solid (solidified under reduced pressure), 0.490 g, yield 21.7%) was obtained.

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.84 (s, 2H, NH), 0.85 (t, J = 6.8 Hz, 24H, CH ₃ ), 1.265−1.375 (m, 64H, CH ₂ ), 1.45−1.505 (m, 16H, CH ₂ ), 1.82-1−1.89 (m, 16H, CH ₂ ), 4.11 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.88 (t, J = 2.2 Hz, 4H, arom.H), 7.36 (d, J = 2.0 Hz, 8H, arom.H), 8.93 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1640.272 (M ⁺ ).

(Production Example 11)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis (3) was prepared according to the same scheme as in Production Example 10 except that 1-bromononane was used instead of 1-bromooctane. Nonyloxy) phenyl] porphyrin (OR of formula [H] is nonyloxy) (red purple solid, 0.392 g, yield 16.6%) was obtained.

(Production Example 12)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis (3) was prepared according to the same scheme as in Production Example 10 except that 1-bromodecane was used instead of 1-bromooctane. Decyloxy) phenyl] porphyrin (OR of formula [H] was decyloxy) (red purple viscous oil, 0.391 g, yield 15.4%) was obtained.

(Production Example 13)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis] was prepared according to the same scheme as in Production Example 10 except that 1-bromoundecane was used instead of 1-bromooctane. (Undecyloxy) phenyl] porphyrin (OR of formula [H] was undecyloxy) (red purple solid, 0.569 g, yield 21.4%) was obtained.

(Production Example 14)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis] was prepared according to the same scheme as in Production Example 10, except that 1-bromododecane was used instead of 1-bromooctane. (Dodecyloxy) phenyl] porphyrin (OR of formula [H] is dodecyloxy) (red purple viscous oil, 0.393 g, yield 13.9%) was obtained.

(Production Example 15)
In Production Example 10, 5,10,15,20-tetrakis [3,5- is prepared according to the same scheme as in Production Example 10 except that 1-bromotridecane was used instead of 1-bromooctane. Bis (tridecyloxy) phenyl] porphyrin (OR of formula [H] is tridecyloxy) (red purple solid, 0.458 g, yield 15.4%) was obtained.

(Production Example 16)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis] was prepared according to the same scheme as in Production Example 10 except that 1-bromotetradecane was used instead of 1-bromooctane. (Tetradecyloxy) phenyl] porphyrin (OR of formula [H] is tetradecyloxy) (red purple solid, 0.594 g, yield 19.0%) was obtained.

(Production Example 17)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis] was prepared according to the same scheme as in Production Example 10 except that 1-bromopentadecane was used instead of 1-bromooctane. (Pentadecyloxy) phenyl] porphyrin (OR of formula [H] is pentadecyloxy) (red purple solid, 0.509 g, yield 15.6%) was obtained.

(Production Example 18)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis] was prepared according to the same scheme as in Production Example 10 except that 1-bromohexadecane was used instead of 1-bromooctane. (Hexadecyloxy) phenyl] porphyrin (OR of formula [H] is hexadecyloxy) (red purple solid, 0.630 g, yield 18.5%) was obtained.

(Production Example 19)
In Production Example 10, 5,10,15,20-tetrakis [3,5- is prepared according to the same scheme as in Production Example 10 except that 1-bromoheptadecane was used instead of 1-bromooctane. Bis (heptadecyloxy) phenyl] porphyrin (OR of formula [H] was heptadecyloxy) (red purple solid, 0.582 g, yield 16.3%) was obtained.

(Production Example 20)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis] was prepared according to the same scheme as in Production Example 10 except that 1-bromooctadecane was used instead of 1-bromooctane. (Octadecyloxy) phenyl] porphyrin (OR of formula [H] is octadecyloxy) (red purple solid, 0.622 g, yield 16.8%) was obtained.

(Comparative Production Example 3)
In Production Example 10, 5,10,15,20-tetrakis [3,5-bis] according to the same scheme as in Production Example 10 except that 1-bromoheptane was used instead of 1-bromooctane. (Heptyloxy) phenyl] porphyrin (OR of formula [H] is heptyloxy) (red purple powder, 0.228 g, yield 12.2%) was obtained.

(Comparative Production Example 4)
According to the same scheme as in Production Example 10, 5,10,15,20-tetrakis [3,5-bis (hexyloxy) phenyl] porphyrin (OR of formula [H] is hexyloxy) (red purple powder, 0.351 g, Yield 20.1%).

About the porphyrin derivative obtained by manufacture examples 10-20 and comparative manufacture examples 3-4, the following thermophysical property evaluation was performed.
Simultaneous differential heat / thermogravimetric measurement (TG-DTA) is performed at a temperature increase rate of 10 K / min in a nitrogen atmosphere using a TG / DTA simultaneous measurement device (product name: DTG-60A, manufactured by Shimadzu Corporation). The temperature was measured from 30 ° C. to 600 ° C., and the weight loss temperature of 2% was defined as the thermal decomposition temperature. Differential scanning calorimetry (DSC) is measured using a differential scanning calorimeter (product name: DSC-60, manufactured by Shimadzu Corporation) at a heating / cooling rate of 10 K / min in a nitrogen atmosphere. The melting point (Tm) and the freezing point (Tf) were measured from -100 ° C to 100 ° C. Considering the possibility that the isolated compound is aggregated, the temperature was raised and cooled three times each. In Comparative Production Example 4, the melting point (Tm) and the freezing point (Tf) were measured from −100 ° C. to 170 ° C. Table 2 shows the results.

Td: thermal decomposition temperature (2% weight loss temperature) / ° C
Tm: Melting point (1st + 2nd + 3rd scan) / ℃
Tc: Crystallization temperature (1st + 2nd + 3rd scan) / ℃
Tm ': Melting temperature after crystallization (1st + 2nd + 3rd scan) / ° C
Tf: Freezing point (1st + 2nd + 3rd scan) / ℃
ND: Not determined or Not observed
br: broadcast peak

  From the results of thermophysical property evaluation, it was found that the derivatives of Production Examples 10 to 18 in which the alkoxy group having an alkyl group having 8 to 16 carbon atoms was substituted had liquid properties at 25 ° C. Among them, a derivative substituted with an alkoxy group having 10 carbon atoms and a derivative substituted with an alkoxy group having 12 carbon atoms were obtained as oily substances. Derivatives substituted with alkoxy groups of 8, 9, 11, 13, 14, 15, and 16 carbon atoms were obtained as solid substances, but may be liquid at 25 ° C by melting once. I understood. In differential scanning calorimetry (DSC), the melting points (second scanning and third scanning of the derivatives substituted with alkoxy groups having 8, 9, 11, 13, 14, 15, and 16 carbon atoms) This is also supported by the fact that Tm) is less than 25 ° C. and the two melting points are within the measurement error range. In general, in differential scanning calorimetry (DSC), the value obtained by the first scan may depend on the preparation method of the measurement sample. Therefore, the thermal properties specific to the substance are determined by the second and subsequent scans. The In this measurement, when the measurement sample is in a solid state, the molecules are condensed and the melting point is measured to be higher in the first scan. However, by melting once, the aggregation of the molecules is suppressed and the second and subsequent times are measured. In the scan, the intrinsic melting point of the substance is considered to have been measured. Derivatives substituted with alkoxy groups having 8, 9, 11, 13, 14, 15, and 16 carbon atoms are obtained as solids with an apparent increase in molecular weight as a result of the interaction of alkyl chains between molecules. It is estimated that

  In addition, the derivatives of Production Examples 19 to 20 in which the alkoxy group having an alkyl group having 17 to 18 carbon atoms is substituted have a melting point (Tm) exceeding 25 ° C., and it is clearly impossible to achieve a liquid state at 25 ° C. However, it turned out that it has liquidity at 26 to 40 degreeC.

Derivatives substituted with an alkoxy group having 15 to 18 carbon atoms have liquidity at 25 ° C. or 26 ° C. to 40 ° C., but the crystallization temperature (Tc) is observed by heating to a higher temperature side. After that, it became clear that the melting temperature (Tm ′) was observed again. It is presumed that the derivative substituted with an alkoxy group having 15 to 18 carbon atoms is more likely to aggregate between molecules than the derivative substituted with an alkoxy group having 8 to 14 carbon atoms.
The derivative of Comparative Production Example 3 in which an alkoxy group having 7 carbon atoms was substituted and the derivative of Comparative Production Example 4 in which an alkoxy group having 6 carbon atoms was substituted were solid at 25 ° C to 40 ° C. The derivative of Comparative Production Example 3 was judged to have amorphous properties from the results of DSC measurement. In addition, the derivative of Comparative Production Example 4 was observed to have a crystallization temperature, and was judged to have crystallinity at a temperature higher than the crystallization temperature and lower than the melting point.

Test _Example: absorption spectral characteristics of _{C 60]}
Since C ₆₀ alone cannot form a film by spin coating, C ₆₀ was dispersed in PMMA, and after forming a film on a quartz substrate as follows, the absorption spectrum of C ₆₀ was measured. The absorption spectrum measurement was performed using a spectrophotometer (UV-2550, manufactured by Shimadzu Corporation).
The quartz substrate used for film formation was washed with a detergent and then washed with pure water. Subsequently, ultrasonic cleaning was performed for 10 minutes each with methanol and acetone, followed by drying under reduced pressure by heating at 60 ° C. for several hours.
The weight ratios are PMMA: C ₆₀ = 99: 1 (1 wt%), 98: 2 (2 wt%), 95: 5 (5 wt%), respectively, and a mixed solution 1 of PMMA and C ₆₀ having a concentration of 100 mg / 3 ml 1 ~ 3 were prepared. The mixed solution was filtered with a 0.2 μm PTFE membrane filter before film formation.
The mixed solutions 1 to 3 were each spin-coated on the washed quartz substrate. The spin coating condition is 2000 rpm / 10 sec. Thereafter, the spin coat film was dried overnight at room temperature under reduced pressure to form a thin film.

Figure 1 shows the absorption spectrum of a thin film of a mixture of PMMA and _{C 60.} For reference, FIG. 1 also shows an absorption spectrum in which only PMMA is thinned. The spectrum is normalized with 1 having the highest absorbance.
As shown in FIG. 1, C ₆₀ has absorption at about 330, 260, 210 nm. PMMA itself has absorption in the ultraviolet region, but its absorbance is small, and it is estimated that the influence of PMMA is low.

<Example 1>
As follows, to obtain a complex consisting of a porphyrin derivative and a C ₆₀ Metropolitan liquid at 40 ° C. or less.
The quartz substrate was cleaned as in the above test example. As the liquid porphyrin derivative, the 5,10,15,20-tetrakis [3,4,5-tris (dodecyloxy) phenyl] porphyrin obtained in Production Example 6 was used, and the toluene solution of the liquid porphyrin derivative having a concentration of 10 mg / 1 ml. Was prepared. Meanwhile, a C ₆₀ toluene solution having a concentration of 1 mg / 1 ml was prepared. Using these solutions, a mixed solution of the liquid porphyrin derivative and C ₆₀ was prepared so that the weight ratio was liquid porphyrin derivative: C ₆₀ = 99: 1 (1 wt%). The mixed solution was filtered with a 0.2 μm PTFE membrane filter before film formation.
The mixed solution was spin-coated on the washed quartz substrate. The spin coating condition is 2000 rpm / 10 sec. Thereafter, the spin coat film was dried overnight at room temperature under reduced pressure to form a thin film (average 60 nm), and a complex composed of a liquid porphyrin derivative and C ₆₀ at 40 ° C. or lower was obtained.

<Example 2>
Example 1 is the same as Example 1 except that the mixed solution of the liquid porphyrin derivative and C ₆₀ is prepared so that the weight ratio is liquid porphyrin derivative: C ₆₀ = 98: 2 (2 wt%). Similarly, to obtain a composite body consisting of a porphyrin derivative and a C ₆₀ Metropolitan liquid at 40 ° C. or less.

<Example 3>
Example 1 is the same as Example 1 except that a mixed solution of the liquid porphyrin derivative and C ₆₀ is prepared so that the weight ratio is liquid porphyrin derivative: C ₆₀ = 95: 5 (5 wt%). Similarly, to obtain a composite body consisting of a porphyrin derivative and a C ₆₀ Metropolitan liquid at 40 ° C. or less.

<Example 4>
Example 1 is different from Example 1 except that a mixed solution of the liquid porphyrin derivative and C ₆₀ is prepared so that the weight ratio is liquid porphyrin derivative: C ₆₀ = 90: 10 (10 wt%). Similarly, to obtain a composite body consisting of a porphyrin derivative and a C ₆₀ Metropolitan liquid at 40 ° C. or less.

[Evaluation 1: Absorption spectrum characteristics]
The absorption spectra of the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10) were measured. The absorption spectrum measurement was performed using a spectrophotometer (UV-2550, manufactured by Shimadzu Corporation).
In FIG. 2, the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10) are normalized with reference to 430 nm. The absorption spectrum was shown. In FIG. 2, for reference, it is also shown as well as the absorption spectrum of the formed thin film, the absorption spectrum of a thin film of a mixture of PMMA and C ₆₀ (1wt%) even using a liquid porphyrin derivative 100% solution.
In FIG. 3, the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10) are normalized based on 655 nm. The absorption spectrum was shown. For reference, FIG. 3 also shows an absorption spectrum of a thin film formed in the same manner using a 100% solution of a liquid porphyrin derivative.

2 is referenced to Soret band, with the addition of C _60, increased absorbance at longer wavelengths, also the absorption maximum of the Soret band, tend to shifts slightly toward shorter wavelengths is observed. On the other hand, in FIG. 3, with the addition of C _60, the intensity of the Soret band was observed a tendency to decrease. 2 and 3, the wavelength of the Soray band includes C ₆₀ absorption, so the tendency of the intensity change of the absorbance does not always match, but even if the reference value is changed, a difference in the spectrum is seen, and the liquid porphyrin derivative and it is clear that the interaction of C ₆₀ are present. From the above, it can be seen that the complex consisting of liquid porphyrin derivative and C ₆₀ Metropolitan at 40 ° C. or less was obtained.

[Evaluation 2: Emission spectrum characteristics]
For the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10), an emission spectrum using 430 nm of the Soray band as excitation light Was measured. The emission spectrum was measured using a spectrofluorometer (F-7000, manufactured by Hitachi High-Technologies Corporation).
In FIG. 4, the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10) are normalized with reference to 660 nm. The emission spectrum is shown. For reference, FIG. 4 also shows the emission spectrum of a thin film formed in the same manner using a 100% solution of a liquid porphyrin derivative.
In FIG. 5, the thin films obtained in Examples 1 to 4 (liquid porphyrin derivative: C ₆₀ (weight ratio) = 99: 1, 98: 2, 95: 5, 90:10) are normalized based on 730 nm. The emission spectrum is shown. For reference, FIG. 5 also shows an emission spectrum of a thin film formed in the same manner using a 100% solution of a liquid porphyrin derivative.

Intensity of the emission spectrum as the increase ratio of the C _60, a strength tends to decrease was observed. However, since the comparison cannot be made only with the emission intensity, the emission intensity at 660 nm and 730 nm is standardized for comparison. Since the 430 nm harmonic wave has a maximum at 860 nm, the spectral intensity on the longer wavelength side from about 760 nm increases, so these intensity increases cannot be compared. FIG. 4 shows a tendency for the emission intensity at 730 nm to increase. On the other hand, in FIG. 5, the emission intensity at 660 nm decreases. These phenomena are presumed that the emission intensity is reduced by functioning as a quencher because C ₆₀ has a strong acceptor property while the liquid porphyrin derivative has a donor property. As described above, since the difference in spectrum with the addition of C ₆₀ even in the emission spectrum was observed, revealed that there is an interaction in porphyrin and C _60, and porphyrin derivatives in a liquid state at 40 ° C. or less it can be seen that the complex consisting of C ₆₀ Metropolitan was obtained.

<Example 5>
As the liquid porphyrin derivative, 5,10,15,20-tetrakis [3,4,5-tris (dodecyloxy) phenyl] porphyrin obtained in Production Example 6 was used, and C ₆₀ was used as a nanocarbon material (Tokyo Chemical Industry). Used). Example 5 The above-mentioned liquid porphyrin derivative and C ₆₀ were mixed while being pressurized in an agate mortar so that the weight ratio would be liquid porphyrin derivative: C ₆₀ = 99: 1 (C ₆₀ content 1 wt%). to obtain a complex consisting of porphyrin derivative is liquid at 40 ° C. below the C ₆₀ Metropolitan.

<Example 6>
In Example 5, except that the amount of the liquid porphyrin derivative and C ₆₀ was changed so that the weight ratio was liquid porphyrin derivative: C ₆₀ = 98: 2 (C ₆₀ content 2 wt%). It was obtained the complex consisting of the porphyrin derivative in a liquid state at less than 40 ° C. example 6 C ₆₀ Prefecture.

<Example 7>
In Example 5, except that the amount of the liquid porphyrin derivative and C ₆₀ was changed so that the weight ratio was liquid porphyrin derivative: C ₆₀ = 95: 5 (C ₆₀ content 5 wt%). It was obtained the complex consisting of the porphyrin derivative in a liquid state at less than 40 ° C. example 7 C ₆₀ Prefecture.

<Example 8>
In Example 5, the weight ratio of liquid porphyrin _derivative: C 60 = _90: so that the 10 _{(C 60} content 10 wt%), except for changing the amount of liquid porphyrin derivative and _{C 60,} as in Example 5 It was obtained the complex consisting of the porphyrin derivative in a liquid state at less than 40 ° C. example 8 C ₆₀ Prefecture.

<Example 9>
In Example 5, the weight ratio of liquid porphyrin _derivative: C 60 = _85: 15 and so that _{(C 60} content 15 wt%), except for changing the amount of liquid porphyrin derivative and _{C 60,} as in Example 5 It was obtained the complex consisting of the porphyrin derivative in a liquid state at less than 40 ° C. example 9 C ₆₀ Prefecture.

<Example 10>
In Example 5, the weight ratio of liquid porphyrin _derivative: C 60 = _80: 20 and so that _{(C 60} content 20 wt%), except for changing the amount of liquid porphyrin derivative and _{C 60,} as in Example 5 It was obtained the complex consisting of the porphyrin derivative in a liquid state at less than 40 ° C. example 10 C ₆₀ Prefecture.

[Evaluation 3: Thermophysical properties]
The composites obtained in Examples 5 to 10 were subjected to differential scanning calorimetry (DSC) measurement. DSC measurement was performed from −100 ° C. to 180 ° C. using a differential scanning calorimeter (product name: DSC204, manufactured by NETZSCH) at a heating / cooling rate of 10 ° C./min in a nitrogen atmosphere. Given the possibility of C ₆₀ are aggregated, it was conducted heating and cooling three times, respectively.
6 to 11 show the results of DSC measurement in which the temperature of the composite obtained in Examples 5 to 10 was increased three times each. 6-11, the peak convex upward represents an endothermic peak. In Figure 6-11, since the result of the second and third scan are matched, through first scan in each of the embodiments, the complex is formed liquid porphyrin derivative and C ₆₀ is uniformly mixed It is suggested that
In the differential scanning calorimetry, since the sample state is usually not stable in the first scan, the second to third scans are used for analysis of thermophysical properties.

In FIG. 12, the vicinity of −10 ° C. of the second scan of DSC measurement of the composite obtained in Examples 5 to 10 (C ₆₀ content: 1, 2, 5, 10, 15, 20 wt%) was enlarged. The results are also shown. For reference, FIG. 12 also shows the results of the second scan of DSC measurement of 100% liquid porphyrin derivative.
FIG. 13 is an enlarged view of the vicinity of 100 ° C. of the second scan of the DSC measurement of the composite obtained in Examples 5 to 10 (C ₆₀ content: 1, 2, 5, 10, 15, 20 wt%). The results are also shown. For reference, FIG. 13 also shows the results of a second scan of DSC measurement of 100% liquid porphyrin derivative.

From FIG. 12 to FIG. 13, as the content of C _{60 in} the liquid porphyrin derivative is increased, the calorific value of the endothermic peak corresponding to the melting point of the liquid porphyrin derivative is decreased, and the melting point is further shifted to the low temperature side. This phenomenon is presumed that the complex becomes an impurity for the liquid porphyrin derivative and exhibits a molar freezing point depression. In the example of content of more than 5 wt% of C _60, endothermic peak presumed to unobserved from complexes with C ₆₀ alone around -20 ℃ ~-10 ℃ was significantly observed, the content of C ₆₀ As the value increased, the peak increased and the peak derived from the porphyrin derivative decreased.
Further, in the examples in which the content of C ₆₀ was 10 wt% or more, an endothermic peak presumed to be derived from a complex that was not observed with a porphyrin derivative and C ₆₀ alone was observed remarkably even at around 100 ° C. This suggested the possibility of the appearance of a liquid crystal phase.

[Evaluation 4: X-ray diffraction measurement]
The composites obtained in Examples 5 to 10 were subjected to X-ray diffraction measurement. X-ray diffraction measurement is performed using a powder X-ray diffractometer (product name: SmartLab, manufactured by Rigaku), tube voltage: 45 kV, tube current: 200 mA, optical system: parallel beam optical system, monochromatization: multilayer mirror, sampling Interval: 0.02 deg, scanning angle: 2 to 40 deg, scanning speed: 4 deg / min, from 30 ° C. to 150 ° C., measurement was performed every 10 ° C. with a holding time of 5 minutes. Given the possibility of C ₆₀ are aggregated and subjected to Atsushi Nobori twice, respectively.

15 and 16 show the first and second temperature rise measurement results of the X-ray diffraction measurement of the composite obtained in Example 8 (C ₆₀ content: 10 wt%), respectively. For comparison, FIG. 17 shows the results of X-ray diffraction measurement at 40 ° C., 100 ° C., 110 ° C., 120 ° C., and 150 ° C. of the porphyrin derivative used alone for the production of the composite. The result of the X-ray-diffraction measurement of 40 degreeC and 150 degreeC of _C60 single used for manufacture of a composite is shown. In FIG. 17, a halo peak presumed to be derived from a porphyrin derivative was observed in the vicinity of 2θ = 3 to 4 °, but the peak intensity hardly changed by heating, and the porphyrin derivative alone was captured by X-ray diffraction measurement by heating. It has been shown that there is no significant structural change. Further, in FIG. 18, it was clarified that no peak is observed in the vicinity of 2θ = 2 to 8 ° with C ₆₀ alone.

Comparing the above measurement results, as shown in FIG. 15, in the first temperature rise measurement of the composite, as the temperature rises, C ₆₀ crystals around 2θ = 11 °, 18 °, 19 °, 21 °. peak derived from the structure is reduced, it is suggested that the crystal structure of C ₆₀ is collapsed by raising the temperature. Further, a broad peak was also observed in the vicinity of 2θ = 3 to 4 °, the peak became sharp up to about 80 ° C., and the peak thereafter became broad. A sharply observed peak around 2θ = 3-4 ° is presumed to be a complex-derived peak. On the other hand, as shown in FIG. 16, in the second temperature rise measurement, new peaks are observed at 2θ = 3.6 °, 6.2 °, 7.2 ° up to 90 ° C., and these peaks are As the temperature increased, it shifted to the low angle side and disappeared between 100 ° C and 110 ° C. New peaks at 2θ = 3.6 °, 6.2 °, and 7.2 ° are presumed to be peaks derived from the complex, suggesting the possibility that the periodic structure of the complex collapses between 100 ° C and 110 ° C. It was. In FIG. 16, the peak derived from the crystal structure of C ₆₀ was observed to be small from the low temperature. In the second heating measurement, for measuring the state of the liquid porphyrin derivative and C ₆₀ are mixed well is started, it is estimated that a peak derived from the complex is strongly observed. It is suggested that the yield of the composite is improved by mixing under pressure and further heating appropriately.

Similar to the DSC measurement, the sample temperature was not stable in the first temperature rise measurement, so the second temperature rise measurement result was used for the analysis of the X-ray diffraction measurement. 19, Example 9 _{(C 60} content: 15 wt%) respectively the second heating measurement results of the X-ray diffraction measurement with. In Example 9 (C ₆₀ content: 15 wt%), the same tendency as in FIG. 16 was observed although there was a difference in strength depending on the C ₆₀ content.

From the above, and the liquid porphyrin derivative and C _60, when mixed under pressure, it is possible to obtain a complex consisting of a porphyrin derivative and a C ₆₀ Prefecture, when heated to improve the yield of the complex However, it is presumed that when the temperature exceeds 100 ° C., the molecular motion becomes intense and the periodic structure of the complex changes. Further, 1 After KaiNoboru temperature to cool, since the liquid porphyrin derivative and C ₆₀ are well mixed, are observed peaks derived from the complex is strong before heating, as well as of the complex becomes more than 100 ° C. It is estimated that the periodic structure changes. The temperature at which the periodic structure changes in the X-ray diffraction measurement was in good agreement with the appearance of an endothermic peak near 100 ° C. in the DSC measurement.
From the above, it has been clarified that the liquid porphyrin derivative functions well as a dispersion medium of C ₆₀ while the liquid porphyrin derivative and C ₆₀ form a complex.

Claims (6)

A composite comprising a porphyrin derivative that is liquid at 40 ° C. or less and a nanocarbon material represented by the following general formula (1).
(In Formula (1), M represents an atom or compound that can be covalently or coordinated to 2H (hydrogen atom) or tetraphenylporphyrin. R ¹ , R ² , and R ³ are each independently hydrogen. An atom or a substituted or unsubstituted alkoxy group, R ^{1 s} , R ^{2 s} , and R ^{3 s} are the same, and R ² and R ³ are substituted or non-substituted having 7 to 15 carbon atoms. R ¹ is a hydrogen atom in a substituted alkoxy group, R ¹ and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms, R ² is a hydrogen atom, or R ¹ and R ² are carbon A substituted or unsubstituted alkoxy group of 7 to 15 and R ³ is a hydrogen atom, R ¹ , R ² and R ³ are a substituted or unsubstituted alkoxy group of 7 to 15 carbon atoms, or R ² has 8 carbon atoms R ¹ and R ³ are hydrogen atoms in a substituted or unsubstituted alkoxy group of -18.   The composite according to claim 1, wherein the nanocarbon material is at least one selected from the group consisting of fullerene and a derivative thereof, carbon nanotube and a derivative thereof, and graphene and a derivative thereof.   In X-ray diffraction spectrum by CuKα ray, selected from the group consisting of 3.6 ° ± 0.2 °, 6.2 ° ± 0.2 °, and 7.2 ° ± 0.2 ° of Bragg angle (2θ) The complex according to claim 1 or 2, which exhibits a diffraction peak in at least one kind. Liquid at 40 ° C. or less represented by the following general formula (1), which has a step of mixing at least a pressure of a porphyrin derivative that is liquid at 40 ° C. or less represented by the following general formula (1) and the nanocarbon material. A method for producing a composite comprising a porphyrin derivative of the above and a nanocarbon material.
(In Formula (1), M represents an atom or compound that can be covalently or coordinated to 2H (hydrogen atom) or tetraphenylporphyrin. R ¹ , R ² , and R ³ are each independently hydrogen. An atom or a substituted or unsubstituted alkoxy group, R ^{1 s} , R ^{2 s} , and R ^{3 s} are the same, and R ² and R ³ are substituted or non-substituted having 7 to 15 carbon atoms. R ¹ is a hydrogen atom in a substituted alkoxy group, R ¹ and R ³ are substituted or unsubstituted alkoxy groups having 7 to 15 carbon atoms, R ² is a hydrogen atom, or R ¹ and R ² are carbon A substituted or unsubstituted alkoxy group of 7 to 15 and R ³ is a hydrogen atom, R ¹ , R ² and R ³ are a substituted or unsubstituted alkoxy group of 7 to 15 carbon atoms, or R ² has 8 carbon atoms R ¹ and R ³ are hydrogen atoms in a substituted or unsubstituted alkoxy group of -18.   A charge transporting material comprising the composite according to any one of claims 1 to 3.   An electronic article comprising the charge transport material according to claim 5.