JP2015218110A - Macrocyclic aromatic amino compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound utilized as a hole transfer agent of an organic EL element with a long emission lifetime and excellent endurance when driven and an all-solid dye-sensitized photoelectric conversion element having high photoelectric conversion efficiency.SOLUTION: There is provided a macrocyclic aromatic amino compound represented by the general formula [I]. (Rand Rare each H or an alkyl group; and Ris H, an alkyl group, an alkoxy group or the like.)

Description

  The present invention relates to a novel macrocyclic aromatic amino compound. More specifically, the present invention relates to a novel macrocyclic aromatic amino compound useful as a hole transfer agent for an all-solid-state dye-sensitized solar cell or an organic EL element.

  Global warming due to the increase in carbon dioxide concentration caused by the use of large amounts of fossil fuels, and the increase in energy demand accompanying population growth are recognized as problems related to the survival of humankind. Therefore, in recent years, the use of sunlight that does not generate infinite and harmful substances has been energetically studied. This clean energy source that is currently in practical use as solar power is inorganic photoelectric conversion using residential single crystal silicon, polycrystalline silicon, amorphous silicon, and inorganic materials such as cadmium telluride and indium copper selenide An element is mentioned.

  However, the inorganic materials used in these inorganic photoelectric conversion elements are required to be high-purity products that require a high-level purification process, and the manufacturing process is complicated due to the structure based on the multilayer pn junction, and the cost is high. Therefore, the development of an element having a simple manufacturing process is required for the spread of photoelectric conversion elements using sunlight.

  While improvement of photoelectric conversion elements using inorganic materials has been promoted, research on organic photoelectric conversion elements using organic materials as simpler elements has been steady. For example, in 1986, Tang et al. Reported a pn junction type organic photoelectric conversion element in which a perylene tetracarboxylic acid derivative that is an n type organic dye and copper phthalocyanine that is a p type organic dye are bonded (for example, Non-Patent Document 1).

  Attempts to greatly increase the effective area of the pn junction where organic thin films are accumulated, or charge separation, in order to improve the short exciton diffusion length and the thinness of the space charge layer, which are considered weak points of organic photoelectric conversion elements Attempts to ensure a sufficient number of organic dyes involved in the process are producing results. An example is a method of performing charge separation throughout the film by dramatically increasing the pn junction by combining an n-type electron conductive organic material and a p-type hole conductive polymer in the film. . In 1995, Heeger et al. Proposed a photoelectric conversion element in which a conjugated polymer is a p-type conductive polymer and fullerene is mixed as an electron conductive material (see, for example, Non-Patent Document 2). This organic photoelectric conversion element has excellent initial performance, but its stability over time is still insufficient.

  On the other hand, in 1991, Gratzel made porous titanium oxide and increased the number of dye molecules that can be separated by charge by adsorbing sensitizing dye on the porous titanium oxide, resulting in high conversion efficiency and stable operation. (See, for example, Non-Patent Document 3). In this dye-sensitized photoelectric conversion element, iodine is used as a hole transfer agent, and an electrolytic solution is required. This dye-sensitized photoelectric conversion element has both a simple manufacturing method and stable prototype reproducibility, and is also called a “dye-sensitized solar cell”, and has attracted great expectations and attention. This dye-sensitized photoelectric conversion element uses a ruthenium (Ru) complex in order to spectrally sensitize titanium oxide. In order to avoid the use of Ru, a noble metal with limited resources, in recent years, inexpensive organic dyes have been proposed, and organic dyes having photoelectric conversion efficiency comparable to Ru complexes have been disclosed (for example, Patent Documents). 1-5).

  In order to effectively use sunlight, it is indispensable to increase the area of the light receiving part and to prepare an outdoor module. However, since the dye-sensitized photoelectric conversion element operates using an electrolyte, Advanced sealing technology that prevents the retention and outflow / dissipation of liquid and iodine is required.

  Development of an all-solid dye-sensitized photoelectric conversion element that avoids such an electrolyte sealing problem and inherits the advantages of the dye-sensitized photoelectric conversion element is also progressing. In this field, those using amorphous organic hole transfer agents (for example, see Non-Patent Document 4) and those using copper iodide as the hole transfer agent (for example, see Non-Patent Document 5) are known. However, it has not yet achieved sufficient photoelectric conversion efficiency and excellent durability.

  In 2005, Gretzel et al. Reported an all-solid dye-sensitized photoelectric conversion element having a relatively good conversion efficiency using a specific organic dye and a hole transfer agent (for example, Non-Patent Document 6). However, there is a need for higher performance all solid dye-sensitized photoelectric conversion elements.

  On the other hand, for organic EL elements, although the theoretical possibilities have been known for the past, the first production of a practical element was reported by Tang et al. Of Kodak in 1987. is there. They separate the light-emitting layer and the hole (hole) transfer layer and stack them with a thin film to improve the light-emitting efficiency of the organic EL device and to enable light emission at a low voltage. (See, for example, Patent Document 6). Since then, many researchers have made researches on improving luminous efficiency and device lifetime, and many compounds have been proposed as device materials. As a result, a material having sufficient utility for light emission characteristics has been developed (see, for example, Patent Document 7). However, it is difficult to say that sufficient characteristics are still obtained with respect to the element lifetime, and the emission luminance decreases with time when the element is driven, and deterioration such as occurrence of a spot where light emission stops called a dark spot is caused. Observed. Recent studies have shown that one of the causes of these deteriorations affecting device lifetime is greatly related to the properties of hole transfer agents. More specifically, the hole transfer agent crystallizes by energization and distorts the uniformity of the thin film to cause a short circuit of the element, and the energization decomposes the hole transfer agent to deteriorate the function and inhibit light emission. It is done.

  In order to solve such a problem of device lifetime, a compound with improved characteristics (common name: α-NPD) has been proposed as a hole transfer agent (see, for example, Patent Document 8).

  Further, recently, a hole transfer material has been found that can provide a device having a higher melting point and a higher thermal decomposition point and a high luminous efficiency (see, for example, Patent Document 9). However, the present situation is that a hole transfer agent having sufficient performance in practical use has not yet been found with respect to stability of light emission luminance and reduction of dark spots.

C. W. Tang, “Two-layer organic photovoltaic cell”, Applied Physics Letters, 48, p. 183 (1986) G. Yu, (4 others), “Polymer Photovoltaic Cells: Enhanced Efficiency via a Network of Internal Donor-Acceptor Heterojunctions”, Science, 270, p. 1789 (1996) B. O'Regan, (1 other), “A low-cost, high-efficiency solar cell based on dyed-sensitive colloidal TiO2 films”, Nature, 353, p. 737 (1991) U. Bach (7 others), “Solid-state dye-sensitized mesoporous TiO2 solar cells with high photo-to-electron conversion efficiency”, Nature, 395, p. 583 (1998) G. R. A. Kumara, (4 others), “Nanocrystalline TiO2 Films for Dye-Sensitized Solid-State Solar Cells”, Key Engineering Materials, 228-229. 119 (2002) L. Schmidt-Mende (7 others), “Organic Dye for Highly Efficient Solid-State Dye-Sensitized Solar Cells”, Advanced Materials, 17, p. 813 (2005)

Japanese Patent No. 4610160 Japanese Patent No. 4326272 Japanese Patent No. 5185517 Japanese Patent No. 5096758 JP 2013-35936 A JP-A 63-295695 JP-A-4-220995 Japanese Patent Laid-Open No. 5-234681 JP 2004-182740 A

  An object of the present invention is to provide a novel macrocyclic aromatic amino acid that is used in an all-solid-state dye-sensitized photoelectric conversion device having high photoelectric conversion efficiency and an organic EL device having excellent durability during driving and a long emission lifetime. It is to provide a compound.

  As a result of intensive studies to achieve the above-mentioned problems, an excellent all-solid-state dye-sensitized photoelectric conversion is achieved by using at least one macrocyclic aromatic amino compound having a specific structure which is a novel compound not described in the literature. An element and an organic EL element were able to be produced.

  That is, the present invention provides a macrocyclic aromatic amino compound represented by the general formula [I].

(In general formula [I], R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and they may be linked to form a cyclopentane ring or a cyclohexane ring. R ₃ represents a substituent on the phenyl ring. And represents a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group.)

  By using the macrocyclic aromatic amino compound of the present invention, it is possible to obtain an all-solid-state dye-sensitized photoelectric conversion device having high photoelectric conversion efficiency, or an organic EL device having excellent durability during driving and a long emission lifetime. it can.

  As a factor of the effect of the present invention, since the macrocyclic aromatic amino compound of the present invention has two rigid fluorene units in one molecule, hole transfer is performed using the macrocyclic aromatic amino compound of the present invention. When a layer is formed, it is presumed that the overlap of π electron orbits between a plurality of adjacent molecules is good and the mobility of holes is high. Furthermore, since the structure formed by a plurality of molecules is excellent in thermal stability, it is presumed that the durability of the element is also excellent.

  The macrocyclic aromatic amino compound represented by the general formula [I] will be described.

In the general formula [I], R ₁ and R ₂ represent a hydrogen atom or an alkyl group. Specific examples of the alkyl group include alkyl groups such as a methyl group, an ethyl group, an n-butyl group, an n-hexyl group, and an n-octyl group. R ₁ and R ₂ may be the same or different. R ₁ and R ₂ may be bonded together to form a cyclopentane ring or a cyclohexane ring. Particularly preferred R ₁ and R ₂ are bonded to each other to form a cyclopentane ring or a cyclohexane ring.

R ₃ is a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group. Examples of the alkyl group include alkyl groups such as a methyl group, an ethyl group, an n-butyl group, an n-hexyl group, and an n-octyl group. Examples of the alkoxy group include alkoxy groups such as methoxy group, ethoxy group, n-butoxy group, n-hexyloxy group, and n-octyloxy group. Examples of the alkylthio group include alkylthio groups such as a methylthio group, an ethylthio group, an n-butylthio group, an n-hexylthio group, and an n-octylthio group. When the alkyl unit of the alkyl group, alkoxy group, or alkylthio group has 3 or more carbon atoms, the alkyl unit may have a straight chain structure or a branched structure.

  Specific examples of the compound of the general formula [I] of the present invention are shown below, but are not limited thereto.

  A typical method for synthesizing the macrocyclic aromatic amino compound of the present invention will be described. For example, it can be synthesized according to the following synthesis scheme using compound a) as a starting material. First, a formylation reaction is performed on compound a) using a reagent such as phosphoryl chloride to isolate compound b). The macrocyclic aromatic amino compound of the present invention can be synthesized by subjecting compound b) to a bimolecular condensation cyclization reaction under basic conditions.

  The details when the macrocyclic aromatic amino compound of the present invention is used as a hole transfer agent for an all-solid dye-sensitized photoelectric conversion element will be described. The all-solid-state dye-sensitized photoelectric conversion element includes a transparent conductive substrate functioning as an anode, an n-type oxide semiconductor layer sensitized by a dye provided on the transparent conductive substrate, a hole transport layer, and a cathode. Consists of a counter electrode.

  The transparent conductive substrate has a conductive layer made of indium-tin composite oxide (hereinafter abbreviated as “ITO”), a metal oxide such as tin oxide doped with fluorine (hereinafter abbreviated as “FTO”) on a glass. It is preferable to use transparent conductive glass deposited on the substrate. For the purpose of reducing the resistance of the transparent conductive glass substrate, a metal lead wire may be used. The material of the metal lead wire is preferably a metal such as aluminum, copper, silver, gold, platinum, or nickel. As a method of installing a metal lead wire, there are a method of installing a metal lead wire on a transparent substrate by vapor deposition, sputtering, etc., and a method of providing ITO or FTO thereon, and a method of installing a metal lead wire on a transparent conductive film.

  Examples of n-type oxide semiconductors include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum oxides. It is most preferable because it is stable both in terms of photochemistry and photochemically, can be produced in various production methods, and fine particles having various particle sizes can be produced. In general, as a method for synthesizing titanium oxide, a method of pyrolyzing titanyl sulfate, a method of producing titanium tetrachloride by burning in the atmosphere, a method of producing organic titanate by hydrothermal decomposition, and the like are known. Yes.

  When the macrocyclic aromatic amino compound of the present invention is used as a hole transfer agent for an all-solid dye-sensitized photoelectric conversion element, the n-type oxide semiconductor is used in a porous state. Titanium oxide particles can be designed relatively freely as long as the particle diameter is 6 nm or more, and this is once dispersed in a solvent, coated in a particle state, formed into a film, surface water When a plurality of adjacent particles are removed and contacted and bonded, a porous body is obtained. In order to ensure sufficient electron conductivity between particles in a porous state, it is necessary to improve the bondability at the grain boundary, and it is common to perform a heat treatment at 400 ° C. or higher. .

  If the particle size of titanium oxide is reduced, the specific surface area increases and the amount of adsorbed dye increases. However, if the particle size is too small, the density of particles in the n-type oxide semiconductor layer increases and hole movement occurs. Bonding with the layer may be hindered. Moreover, since the film shrinkage may be caused at the time of heating film formation, the particle diameter is preferably 15 nm or more. Further, the thickness of the deposited n-type oxide semiconductor layer is preferably 0.1 μm to 10 μm, and particularly preferably 0.5 μm to 5 μm. When the film thickness of the n-type oxide semiconductor layer is less than 0.1 μm, the amount of dye adsorbed is insufficient and the incident light cannot be efficiently absorbed, resulting in a decrease in photoelectric conversion efficiency. There is. When the film thickness exceeds 10 μm, the internal resistance of the n-type oxide semiconductor layer increases, so that the total photoelectric conversion efficiency may decrease.

  It is preferable to have a titanium oxide blocking layer having a thickness of 0.1 μm to 5.0 μm at the interface between the transparent conductive substrate and the n-type oxide semiconductor layer. When the thickness of the titanium oxide blocking layer is less than 0.1 μm, the conversion efficiency may be lowered because the blocking effect is lowered. If the thickness of the titanium oxide blocking layer exceeds 5.0 μm, the internal resistance in the titanium oxide blocking layer increases, and the conversion efficiency may decrease.

  Regarding the production method of the titanium oxide blocking layer, it is possible to use a method of coating film formation → thermal decomposition → titanium oxide blocking layer formation using a solution of a thermally decomposable titanium EDTA (ethylenediaminetetraacetic acid) complex. This is preferable because a titanium oxide blocking layer having a uniform thickness can be formed.

  As a method for sensitizing a porous n-type oxide semiconductor layer with a dye, a method of immersing the n-type oxide semiconductor layer in an organic solvent in which the dye is dispersed or dissolved is generally used. The dye used usually has an acidic group having a pKa of less than 6, which functions as an adsorbing functional group on the n-type oxide semiconductor layer. A co-adsorbent typified by a steroid compound may be used in combination to protect the dye adsorption state and the non-adsorbed portion of the dye on the surface of the n-type oxide semiconductor layer.

  Particularly preferred dyes include, but are not limited to, the following.

  When the macrocyclic aromatic amino compound of the present invention is used as a hole transfer agent for an all-solid dye-sensitized photoelectric conversion element, it is dissolved in an organic solvent such as toluene or tetrahydrofuran (THF), and the solution is increased with a dye. A hole transport layer is formed by coating on the sensed n-type oxide semiconductor layer. Part of the hole transfer agent is also filled in the porous structure of the n-type oxide semiconductor layer, and contributes to the exchange of holes with the dye adsorbed on the n-type oxide semiconductor layer. When forming the hole moving layer, a resin can be used in combination. As such a resin, polystyrene resin, aromatic polycarbonate resin, and the like are excellent from the viewpoints of solubility in a solvent, transparency, and film formability. The amount of resin used is preferably 0.1% by mass to 20% by mass with respect to the hole transfer agent, but if the amount of resin is too large, the hole mobility in the hole transfer layer may be lowered. The amount of resin is particularly preferably 10% by mass or less with respect to the hole transfer agent.

  Holes are injected from the hole transfer agent into the counter electrode which is the cathode. Specific examples of the material used for the counter electrode include noble metals such as platinum, gold, and silver, and graphite-based conductive carbon electrodes. A metal or carbon electrode can be produced by vapor deposition in a vacuum, but the carbon electrode can also be produced by dispersing and applying fine particles such as acetylene black which is conductive graphite.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these at all.

(Synthesis Example 1: Synthesis of Macrocyclic Aromatic Amino Compound (A-9))
Compound C was converted to Compound D according to a standard method. 3.8 g of compound D was dissolved in 60 ml of THF, and 2.9 g of potassium t-butoxide was added with stirring under ice cooling, followed by stirring at room temperature for 2 hours. THF was distilled off from the reaction solution under reduced pressure using a rotary evaporator, and the residue was washed with 50 ml of water and collected by filtration. The crude product was purified by silica gel column chromatography using a mixed solvent of chloroform / cyclohexane = 3/2 as a developing solvent, and the developing solvent was distilled off under reduced pressure with a rotary evaporator to obtain a macrocyclic aromatic amino compound (A-9). 0.9 g of a pale yellow solid was isolated.

¹ H-NMR spectrum (CDCl ₃ solution): δ (ppm) 8.45 (2H, s, CH), 7.96 (2H, d, Ph), 7.71 to 7.58 (8H, m, Ph) ), 7.73-7.13 (6H, m, Ph), 7.13 (2H, s, Ph), 7.00 (2H, d, Ph), 4.70 (2H, s, CH), 3.85 (2H, s, CH), 2.03-1.47 (12H, m, CH2)

(Synthesis Example 2: Synthesis of Macrocyclic Aromatic Amino Compound (A-11))
Compound E was converted to Compound F according to a standard method. 3.0 g of compound F was dissolved in 60 ml of THF, and 2.9 g of potassium t-butoxide was added with stirring under ice cooling, followed by stirring at room temperature for 2 hours. THF was distilled off from the reaction solution under reduced pressure using a rotary evaporator, and the residue was washed with 50 ml of water and collected by filtration. The crude product was purified by silica gel column chromatography using chloroform as a developing solvent, and the developing solvent was distilled off under reduced pressure with a rotary evaporator to isolate 0.3 g of a macrocyclic aromatic amino compound A-11 vermilion solid.

¹ H-NMR spectrum (CDCl ₃ solution): δ (ppm) 7.98 (2H, s, CH), 7.67 to 7.54 (12H, d, Ph), 7.15 (4H, s, Ph) ), 7.03 (2H, s, Ph), 5.01 (2H, s, CH), 3.85 (2H, s, CH), 2.58 (6H, s, SCH3), 2.06- 1.50 (12H, m, CH2)

  Next, although the Example of the compound of this invention is demonstrated further in detail, this invention is not limited to these at all. In the application examples, unless otherwise specified, the number of parts and the percentage are based on mass.

Example 1
<Preparation of dye-sensitized solar cell>
An ethanol solution of titanium EDTA complex (manufactured by Nagase Chemtech Co., Ltd., trade name: EOLID (registered trademark)) is applied onto an FTO glass substrate (transparent conductive substrate), and baked at 450 ° C. for 1 hour, whereby an FTO glass substrate is obtained. A titanium oxide blocking layer having a thickness of 0.2 μm was formed thereon. Next, 4 parts of titanium oxide (manufactured by Nippon Aerosil Co., Ltd., trade name: P-25) is dispersed in 13 parts of ethanol / isopropanol mixed solvent (volume ratio = 1: 1) using a paint conditioner (manufactured by Red Devil). A dispersion was prepared, and 0.5 parts of concentrated nitric acid was added to 10 parts of the dispersion to prepare a paste. This paste was applied onto an FTO glass substrate provided with a titanium oxide blocking layer, and baked at 450 ° C. for 1 hour, so that an FTO glass substrate provided with an n-type oxide semiconductor layer having a thickness of 1.0 μm (semiconductor electrode) ) Was produced.

  The dye shown in the exemplified dye (B-1) was dissolved in a mixed solution of t-butanol / acetonitrile (volume ratio: 1/1) to prepare a dye solution having a concentration of 0.5 mM. The semiconductor electrode prepared previously was immersed in this dye solution for 3 hours at room temperature to perform an adsorption treatment, thereby preparing a working electrode in which the n-type oxide semiconductor layer on the FTO substrate was sensitized with the dye.

Next, 1 part of the macrocyclic aromatic amino compound (A-9) of the present invention is dissolved in 99 parts of toluene and spin-coated on the n-type oxide semiconductor layer sensitized with the dye of the working electrode. A 0.5 μm hole transport layer was formed. Further, gold having a film thickness of 60 μm was deposited by a vacuum deposition method, and the counter electrode was accumulated to produce an all-solid-state dye-sensitized photoelectric conversion element. The electrode area was 1 cm ² .

(Examples 2 to 20)
An all-solid dye-sensitized photoelectric conversion element was produced in the same manner as in Example 1 except that the macrocyclic aromatic amino compound (A-9) used as the hole transfer agent was changed to the compounds shown in Table 1.

(Comparative Examples 1-2)
An all-solid dye-sensitized photoelectric conversion element was produced in the same manner as in Example 1 except that the hole transfer agent (A-9) was changed to comparative hole transfer agents (G-1) to (G-2).

<Evaluation: Photoelectric conversion efficiency>
Irradiated from the semiconductor electrode side of the device was simulated sunlight (AM1.5G, irradiation intensity 100 mW / cm ² ) generated from a solar simulator (manufactured by Yamashita Denso Co., Ltd., device name: YSS-40S) as a light source, and electrochemical The photoelectric conversion efficiency of the all-solid-state dye-sensitized photoelectric conversion elements of Examples 1 to 20 and Comparative Examples 1 to 2 was evaluated using a measuring device (manufactured by Solartron, device name: SI-1280B). The results are shown in Table 1. The open circuit voltages, short circuit current densities, and photoelectric conversion efficiencies of Examples 1 to 20 and Comparative Example 2 are shown as relative values based on the evaluation results of Comparative Example 1.

(Example 21)
An all-solid dye-sensitized photoelectric conversion element was produced in the same manner as in Example 1 except that the exemplified dye (B-1) was changed to the exemplified dye (B-2).

(Examples 22 to 40)
An all-solid dye-sensitized photoelectric conversion element was produced in the same manner as in Example 21, except that the macrocyclic aromatic amino compound (A-9) used as the hole transfer agent was changed to the compounds shown in Table 2.

(Comparative Examples 3-4)
An all-solid dye-sensitized photoelectric conversion element was produced in the same manner as in Example 21 except that the hole transfer agent (A-9) was changed to comparative hole transfer agents (G-1) to (G-2).

  In the same manner as in Examples 1 to 20 and Comparative Examples 1 and 2, the photoelectric conversion efficiencies of the all solid dye-sensitized photoelectric conversion elements prepared in Examples 21 to 40 and Comparative Examples 3 to 4 were evaluated. The results are shown in Table 2. The open circuit voltage, short circuit current density, and photoelectric conversion efficiency of Examples 21 to 40 and Comparative Example 4 are shown as relative values based on the evaluation results of Comparative Example 3.

(Examples 41 to 42)
The macrocyclic aromatic amino compound of the present invention was used as a hole transfer agent for an organic EL device, and its function was confirmed. In Example 41, the organic EL device is a thin film of the macrocyclic aromatic amino compound (A-9) of the present invention as a hole transfer agent on a transparent electrode in which an ITO electrode is previously formed on a glass substrate. In Example 42, a thin film of the macrocyclic aromatic amino compound (A-11) of the present invention was formed, an aluminum quinoline trimer thin film was formed thereon as a light emitting layer and an electron transport layer, and Mg was further formed thereon. / Al electrode thin film was formed.

When an electric current of 100 mA / cm ² was applied to the organic EL element produced as described above using a constant current device, it was confirmed that the organic EL element emitted light continuously with sufficient light emission luminance. When any of the exemplified compounds was used, the light emission lifetime until the initial light emission intensity was halved was 100 hours or longer.

(Comparative Example 5)
Organic EL devices similar to those in Examples 41 to 42 were produced using α-NPD instead of the macrocyclic aromatic amino compound (A-9) as the hole transfer agent. When a current of 100 mA / cm ² was applied using a constant current device, light was emitted with sufficient light emission brightness at first, but the light emission lifetime was shorter than that of the exemplified compound, and was about 50 hours.

  The macrocyclic aromatic amino compound of the present invention can be used as a hole transfer agent for an all-solid dye-sensitized photoelectric conversion element or an organic EL element. Further, it can be utilized for a hole transfer agent such as an optical sensor sensitive to light of a specific wavelength.

Claims (1)

Macrocyclic aromatic amino compounds represented by the following general formula [I].
(In general formula [I], R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and they may be linked to form a cyclopentane ring or a cyclohexane ring. R ₃ represents a substituent on the phenyl ring. And represents a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group.)