Photoelectric conversion film and method for producing phthalocyanine compound

Abstract

To provide a phthalocyanine compound that absorbs and emits near infrared light, a film and a method for producing a phthalocyanine compound.SOLUTION: A phthalocyanine compound is represented by the following formula (1), where M represents two hydrogen atoms, a central element, or a central element coordinated with an axial ligand; R1 each represents a phenyl group, a naphthyl group, a group that comprises a heterocycle comprising nitrogen, or a partially substituted group of them; R2 each denotes hydrogen, an aryl group, an alkyl group with 6 or less carbon atoms, or a partially substituted group of them; and R3 each represents hydrogen.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides Photoelectric conversion The present invention relates to a method for producing a film and a phthalocyanine compound. [Background technology]

[0002] Materials that can absorb and emit near-infrared light with a wavelength of about 1 μm are expected to be used in medicine, sensors, and other fields.

[0003] For example, Patent Documents 1 and 2 and Non-Patent Document 1 describe phthalocyanine compounds that absorb and emit light in the near infrared region. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-176126 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-103911 [Non-patent literature]

[0005] [Non-Patent Document 1] Taniyuki Furuyama, Koh Satoh, Tomofumi Kushiya, and Nagao Kobayashi. J. Am. Chem. Soc. 2014, 136, 765-776. Summary of the Invention [Problem to be solved by the invention]

[0006] However, the number of materials that absorb and emit light in the near-infrared region is still limited, and further development is required. There is also a need to develop materials that allow the absorption and emission wavelengths to be selected by introducing metal elements, etc.

[0007] The present invention has been made in view of the above problems, and an object of the present invention is to provide a phthalocyanine compound, a film, and a method for producing the phthalocyanine compound that absorbs and emits near-infrared light. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention provides the following means.

[0009] (1) The phthalocyanine compound according to the first embodiment is represented by the following formula (1).

[0010] [ka]

[0011] In the formula, M is two hydrogen atoms, a central element, or a central element coordinated with an axial ligand; R1 is a phenyl group, a naphthyl group, a group having a nitrogen-containing heterocycle, or a group in which any of these is partially substituted; R2 is a hydrogen atom, an aryl group, an alkyl group having 6 or less carbon atoms, or a group in which any of these is partially substituted; and R3 is a hydrogen atom.

[0012] (2) The film according to the second embodiment contains the phthalocyanine compound according to the above embodiment.

[0013] (3) A method for producing a phthalocyanine compound according to the third embodiment includes a step of synthesizing a precursor represented by the following formula (2) and a step of reacting the precursor.

[0014] [ka] [Effects of the Invention]

[0015] The phthalocyanine compound and film according to the above embodiment can absorb and emit near-infrared light. The method for producing a phthalocyanine compound according to the above embodiment can produce a phthalocyanine compound capable of absorbing and emitting near-infrared light. [Brief explanation of the drawings]

[0016] [Figure 1] 1 shows the reaction formula of the precursor in Example 1. [Figure 2] The reaction formula of the phthalocyanine compound in Example 1 is shown below. [Figure 3] 1 shows the absorption spectrum of a phthalocyanine compound in an example. [Figure 4] 1 shows the absorption spectrum of a phthalocyanine compound in an example. [Figure 5] 1 shows the absorption spectrum of a phthalocyanine compound in an example. [Figure 6] 1 shows the emission spectrum of a phthalocyanine compound in an example. [Figure 7] 1 shows the optical properties of a dispersion film containing a phthalocyanine compound in an example. [Figure 8] The reaction formula of the phthalocyanine compound in Example 11 is shown below. [Figure 9] FIG. 1 is a diagram summarizing the phthalocyanine compounds evaluated in each example. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present embodiment will be described in detail below. The following description is an example of the present invention, and the present invention is not limited thereto, and can be implemented with appropriate modifications within the scope of the present invention.

[0018] "Phthalocyanine compounds" The phthalocyanine compound according to this embodiment is represented by the following formula (1).

[0019] [ka]

[0020] In the above formula (1), M is two hydrogen atoms, a central element, or a central element coordinated with an axial ligand. When two hydrogen atoms are coordinated to M, the compound of formula (1) is represented by the following formula (1A).

[0021] [ka]

[0022] The central element is, for example, a metal element. Examples of the central element include Mg, Si, P, Mn, Fe, Co, Ni, Cu, Zn, Ru, Pd, and Sn. Some of the central elements are arranged at the central position with an axial ligand L coordinated thereto. The central element, which is a ligand, is located at the π-π position of the phthalocyanine compound. * This affects the transition. When the central element is changed, the peak wavelength of light absorption changes.

[0023] The compound of formula (1) when an axial ligand L is coordinated to the central element is represented by the following formula (1B): The central element M is present on the same plane as the phthalocyanine ring, and the axial ligand L is positioned at a position intersecting the plane on which the phthalocyanine ring exists.

[0024] [ka]

[0025] The number of axial ligands L varies depending on the central element M. The number of axial ligands L is, for example, 0, 1, or 2.

[0026] For example, when the central element M is Mg, Ni, Cu, Zn, Pd, or the like, the number of axial ligands L is 0. In other words, the central element M does not have an axial ligand L.

[0027] For example, when the central element is Mn, there is one axial ligand L. In this case, the axial ligand L is, for example, Cl or OAc. Ac is an acetyl group.

[0028] Furthermore, for example, when the central element is Fe or Co, the number of axial ligands L is 0 or 1. In this case, the axial ligand L is, for example, Cl or OAc.

[0029] Furthermore, for example, when the central element is Si, P, or Sn, the number of axial ligands L is two. When the central element is Si or Sn, the axial ligand L is, for example, OH, Cl, or OR. When the central element is P, the axial ligand L is, for example, OH, Cl, Br, or OR. R is an alkyl group having 6 or less carbon atoms or a benzene derivative, and the benzene derivative may be substituted with any substituent. When there are two or more axial ligands L, the respective axial ligands L may be different.

[0030] For example, when the central element is Ru, the number of axial ligands L is 1 or 2. When the central element is Ru, the axial ligand L is, for example, pyridine, a compound in which the hydrogen attached to a carbon constituting pyridine is substituted with the above-mentioned R, benzonitrile, a compound in which the hydrogen attached to a carbon constituting benzonitrile is substituted with the above-mentioned R, R'CN, or CO. R' is an alkyl group having 6 or less carbon atoms.

[0031] Depending on the central element, a counter anion that compensates for the charge of the entire phthalocyanine compound may be present in the system. For example, when the central element is P, OH may be used as the counter anion. - , Cl - , PF6 - , ClO4 - The system may have any one of the above.

[0032] R1 in the above formulas (1), (1A), and (1B) is a phenyl group, a naphthyl group, a group having a nitrogen-containing heterocycle, or a group in which these are partially substituted. A "group in which these are partially substituted" refers to a group in which some of the hydrogen atoms connected to the elements constituting the ring have been replaced with other elements, such as a substituted phenyl group or a substituted naphthyl group. For example, this refers to a group in which some of the hydrogen atoms connected to the carbon atoms constituting the phenyl ring have been replaced with hydroxyl groups or alkyl groups. There are eight R1s in one phthalocyanine compound, and each R1 may be the same or different.

[0033] R2 in the above formulas (1), (1A), and (1B) is hydrogen, an aryl group, an alkyl group having 6 or less carbon atoms, or a group in which any of these groups is partially substituted. There are eight R2s in one phthalocyanine compound, and each R2 may be the same or different.

[0034] In the above formulas (1), (1A), and (1B), R3 is hydrogen. Modification of R3 affects the molecular orbital of the phthalocyanine compound, shifting the absorption and emission wavelengths of the phthalocyanine compound. As a result, the phthalocyanine compound may no longer absorb or emit light in the desired wavelength range.

[0035] Next, a method for producing the phthalocyanine compound according to this embodiment will be described. The method for producing the phthalocyanine compound according to this embodiment includes a step of synthesizing a precursor and a step of reacting the precursor.

[0036] First, a precursor represented by the following formula (2) is synthesized.

[0037] [ka]

[0038] First, the first compound, the second compound, a metal salt of the catalyst, a ligand of the catalyst, and a deprotonating agent were added to a solvent, and the mixture was stirred while being heated and refluxed.

[0039] The first compound is represented by, for example, the following formula (3): X is a halogen. For example, 3,6-diiodophthalonitrile, in which X is iodine, can be used as the first compound.

[0040] [ka]

[0041] The second compound is, for example, an element that substitutes for the halogen in the above formula (3). A part of the second compound becomes R1 of the phthalocyanine compound according to this embodiment. For example, when R1 is a phenyl group, aniline is used.

[0042] Examples of the metal salt of the catalyst include palladium acetate and tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3). The metal salt of the catalyst acts, for example, to interact with the ligand of the catalyst and appropriately link the first compound and the second compound.

[0043] Examples of the ligand of the catalyst include 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP). The ligand of the catalyst interacts with the metal salt of the catalyst to properly link the first compound and the second compound.

[0044] Examples of the deprotonating agent include cesium carbonate and potassium carbonate. The base acts to activate an intermediate in the linking reaction between the first compound and the second compound, for example.

[0045] The solvent is, for example, toluene or 1,4-dioxane.

[0046] Next, after the reaction solution is cooled to room temperature, water is added to the reaction solution to stop the reaction. The organic layer is then extracted from the reaction solution and dried to produce a crude product. The crude product is then purified to produce a first precursor. The crude product is purified, for example, by chromatography. The first precursor is represented, for example, by the following formula (4). When R2 of the phthalocyanine compound to be produced is hydrogen, the phthalocyanine compound is produced using the first precursor.

[0047] [ka]

[0048] Next, if necessary, a portion of the first precursor is substituted by adding the first precursor, a substitution product, and a deprotonating agent to a solution, and then heating and stirring the mixture.

[0049] The substituent is, for example, an iodide of R2. For example, when R2 is a methyl group, it is methyl iodide. The deprotonating agent is, for example, potassium carbonate. The deprotonating agent may be sodium hydride instead of potassium carbonate. The solution is, for example, N,N-dimethylformamide (DMF). The solvent may be tetrahydrofuran (THF) instead of DMF.

[0050] Next, after cooling the reaction solution to room temperature, water is added to the reaction solution to stop the reaction. The organic layer is then extracted from the reaction solution and dried to produce a crude product. The crude product is then purified. The crude product is purified, for example, using chromatography. In the above procedure, the hydrogen in formula (4) is replaced with another group to obtain a precursor of formula (2).

[0051] Next, the precursor is reacted to produce a desired phthalocyanine compound. The step of producing a phthalocyanine compound from the precursor can be carried out by a known method.

[0052] For example, the precursor is added to a lithium hexoxide solution and stirred while heating. After the reaction solution is cooled, the mixture is extracted. The extracted organic layer is washed, dried, and filtered to produce a crude product. The crude product is washed with an organic solvent to obtain a first phthalocyanine compound. The first phthalocyanine compound is represented by the above formula (1A). The first phthalocyanine compound corresponds to the formula (1) where M is two hydrogen atoms.

[0053] Next, if necessary, an element is coordinated to the center of the first phthalocyanine compound. The coordination of the element is carried out by adding the first phthalocyanine compound and a compound containing the coordinated element to a solution, and heating and stirring. The reaction solution is then cooled, and the mixture is extracted. The extracted organic layer is then washed, dried, and filtered to produce a crude product. The crude product is then separated and purified to obtain the phthalocyanine compound represented by formula (1).

[0054] Here, an example of a method for producing a phthalocyanine compound represented by formula (1) has been described. The method for producing this phthalocyanine compound is not limited to this example. For example, in the above example, after producing a first phthalocyanine compound represented by formula (1A), an element is coordinated at the center. However, the phthalocyanine compound represented by formula (1) may be produced directly from the first precursor by reacting the first precursor with a compound containing the central element.

[0055] The phthalocyanine compound according to this embodiment has absorption and emission spectrum peaks in the long wavelength region of 800 nm or more. Furthermore, the phthalocyanine compound according to this embodiment hardly absorbs light in the visible wavelength region of 350 nm to 780 nm, and hardly emits light in this region. Therefore, the phthalocyanine compound according to this embodiment is transparent in the visible wavelength region. The phthalocyanine compound according to this embodiment is applicable to a variety of uses.

[0056] For example, the compound can be used in dye-sensitized solar cells. The compound's absorption of light in the wavelength range longer than visible light improves the power generation efficiency of the dye-sensitized solar cell. Furthermore, for example, the compound can also be used as a hydrogen production catalyst. The compound's absorption of light in the wavelength range longer than visible light increases the catalytic reaction efficiency. Furthermore, for example, the compound can also be used as a sensitizer for photodynamic therapy and photoimmunotherapy. The compound's absorption of light in the wavelength range longer than visible light, which has high biological permeability, increases the efficiency of treating deep tissues that cannot be reached by visible light. Furthermore, for example, the compound can also be used as a contrast agent for photoacoustic imaging. The compound's absorption of light in the wavelength range longer than visible light increases the efficiency of the contrast agent.

[0057] Furthermore, for example, a phthalocyanine compound can be used in a film. The film is, for example, a film in which a phthalocyanine compound is dispersed in a resin. This film is transparent in the visible light wavelength range and is expected to be applied to various uses. For example, the film can be used to provide a near-infrared photoelectric conversion element that selectively responds to the near-infrared light range.

[0058] The resin is not particularly limited. Examples of the resin include acrylic resin, polycarbonate resin, olefin resin, polystyrene resin, polyester resin, polyamide resin, silicone resin, thermoplastic elastomer, butyl rubber, nitrile rubber, silicone rubber, etc. For example, acrylic resin (polymethyl methacrylate (PMMA)) has excellent optical properties and is easily applied to optical components.

[0059] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the specific embodiments, and various modifications and changes are possible within the scope of the gist of the present invention as set forth in the claims. [Example]

[0060] Example 1 "Preparation of precursors" In Example 1, the reaction shown in FIG. 1 was carried out to produce a precursor.

[0061] <Preparation of the first precursor> First, 3,6-diiodophthalonitrile (444.4 mg, 1.2 mmol), palladium acetate (18.4 mg, 82 μmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) (70.0 mg, 0.17 mmol), cesium carbonate (1.37 g, 4.2 mmol), and aniline (93.1 mg, 3.5 mmol) were dissolved in toluene (2 mL) under an argon atmosphere and stirred for 2.5 hours under reflux.

[0062] The reaction solution was then cooled to room temperature, and water was added to quench the reaction. The mixture was then extracted from the reaction solution using ethyl acetate. The organic layer of the extracted mixture was washed with water and saturated brine, and then dried using sodium sulfate. The solid was then removed by filtration, and the solution was concentrated to obtain a crude product. This crude product was then purified by silica gel flash column chromatography (developing solvent, hexane:ethyl acetate = 2.5:1). After purification, 307.1 mg of a yellow solid was obtained. The yield was 82%.

[0063] Next, the molecular structure of the obtained yellow solid crystal was measured using NMR (nuclear magnetic resonance) under the following conditions, and elemental analysis was also performed using high-resolution mass spectrometry. 400 MHz 1 H NMR (CDCl3) δ (ppm) 7.36-7.32 (m, 4H), 7.32 (s, 2H), 7.13-7.08 (m, 6H). 125 MHz 13 C{ 1 H} NMR (CDCl3) δ (ppm): 141.8, 140.0, 129.9, 124.3, 122.2, 121.0, 114.9, 100.1. HR-APCI-FT-ICR-MS calculation for C 20 H 15 N4[M+H] + : 311.1291, found 311.1289.

[0064] As a result, it was confirmed that the first precursor represented by chemical formula I in FIG. 1 was obtained.

[0065] <Preparation of the second precursor> Next, this compound I (26.5 mg, 0.084 mmol), methyl iodide (0.1 mL), and potassium carbonate (58.8 mg, 0.44 mmol) were dissolved in DMF (4 mL) under an argon atmosphere. The solution was stirred at 130 °C for 2 days. After the reaction solution was cooled to room temperature, water was added to quench the reaction. The mixture was extracted with ethyl acetate, and the organic layer was washed with water and saturated brine. The washed sample was then dried over sodium sulfate, the solid was removed by filtration, and the solution was concentrated to obtain the crude product. The crude product was then purified by silica gel flash column chromatography (eluent, hexane:ethyl acetate = 2:1). After purification, 26.2 mg of a yellow solid was obtained. The yield was 91%.

[0066] Next, the molecular structure of the obtained yellow solid crystal was measured using NMR (nuclear magnetic resonance) under the following conditions, and elemental analysis was also performed using high-resolution mass spectrometry. 400 MHz 1 H NMR (CDCl3) δ (ppm): 7.34-7.28 (m, 4H), 7.31 (s, 2H), 7.04-7.00 (m, 2H), 6.94-6.91 (m, 4H), 3.44 (s, 6H).125 MHz 13 C{ 1 H} NMR (CDCl3) δ (ppm): 148.8, 147.5, 130.6, 129.5, 122.2, 118.8, 114.5, 111.9, 41.0. HR-APCI-FT-ICR-MS calculation for C 22 H 19 N4[M+H] + : 339.1604, found 339.1602.

[0067] As a result, it was confirmed that the second precursor represented by chemical formula II in FIG. 1 was obtained.

[0068] "Preparation of phthalocyanine compounds" Next, a phthalocyanine-based compound was prepared using the second precursor represented by Chemical Formula II.

[0069] <Preparation of First Phthalocyanine Compound> First, under an argon atmosphere, lithium metal (19.5 mg, 2.8 mmol) was added to 1-hexanol (3 mL) and heated to reflux until the lithium metal was consumed, preparing a lithium hexoxide solution. Then, the second precursor (201.6 mg, 0.60 mmol) represented by formula II was quickly added to this solution and stirred at 150 °C for 2 hours. After cooling to room temperature, the mixture was extracted with chloroform. The organic layer of the extracted mixture was washed with water and saturated brine. The washed sample was then dried over sodium sulfate, the solid was removed by filtration, and the solution was concentrated to obtain the crude product. The resulting crude product was then washed with methanol and then hexane. The sample was then dried to obtain 103.2 mg of a dark green solid. The yield was 51%.

[0070] Next, the molecular structure of the obtained dark green solid crystal was measured using NMR (nuclear magnetic resonance) under the following conditions, and elemental analysis was also performed using high-resolution mass spectrometry. 400 MHz 1 H NMR (CDCl3) δ (ppm): 7.66 (s, 8H), 7.24-7.20 (m, 16H), 6.94-6.91 (m, 24H), 3.43 (s, 24H). HR-MALDI-FT-ICR-MS calcd for C 88 H 74 N 16 [M] + : 1354.6277, found 1354.6289. UV-vis-NIR (CHCl3) λ max nm (ε x 10- 4): 896 (8.7), 791sh (3.7), 497 (1.1), 337 (9.7). λ F, max (CHCl3): 972 nm. Φ F = 0.001.

[0071] As a result, it was confirmed that the first phthalocyanine compound represented by chemical formula III in FIG. 2 was obtained.

[0072] <Preparation of second phthalocyanine compound> Next, a substitution step was performed to replace the two hydrogen atoms at the center of the first phthalocyanine compound with other elements and coordinate the central element. The first phthalocyanine compound (13.3 mg, 10 μmol) represented by chemical formula III and zinc acetate (15.6 mg, 85 μmol) were dissolved in DMF (1 mL) and stirred at 150°C for 3 hours. After cooling the reaction solution to room temperature, the mixture was extracted with chloroform. The organic layer of the mixture was washed with water and saturated brine. The washed sample was then dried over sodium sulfate, the solid was removed by filtration, and the solution was concentrated to obtain a crude product. The crude product was then purified by silica gel column chromatography (developing solvent: chloroform) to obtain 7.3 mg of a dark green solid. The yield was 54%.

[0073] Next, the molecular structure of the obtained dark green solid crystal was measured using NMR (nuclear magnetic resonance) under the following conditions, and elemental analysis was also performed using high-resolution mass spectrometry. 500 MHz 1 H NMR (pyridine-d5) δ (ppm): 7.78 (s, 8H), 7.40-7.37 (m, 16H), 7.15-7.11 (m, 24H), 3.81 (s, 24H). HR-MALDI-FT-ICR-MS calcd for C 88 H 72 N 16 Zn [M] + : 1416.5412, found 1416.5431. UV-vis-NIR (CHCl3) λmax nm (ε x 10 -4 ): 844 (5.1), 748sh (1.9), 332 (5.3). F, max (CHCl3): 919 nm. Φ F = 0.003.

[0074] As a result, it was confirmed that the second phthalocyanine compound represented by chemical formula IV in Figure 2 was obtained. That is, the central element M of the phthalocyanine compound of Example 1 was Zn.

[0075] "evaluation" Next, the prepared second phthalocyanine compound was evaluated. The absorption spectrum and emission spectrum of the second phthalocyanine compound were measured. A chloroform solution of the crystals was prepared and the absorption spectrum and emission spectrum were measured. The measurement results are shown in Figs. 3 to 6. Figs. 3 to 5 show the absorption spectra of the phthalocyanine compounds according to the examples described later, and Fig. 6 shows the emission spectra of the phthalocyanine compounds according to some of the examples described later. The peak wavelength of the absorption spectrum of the phthalocyanine compound of Example 1 was 844 nm, and the peak wavelength of the emission spectrum was 919 nm.

[0076] The second phthalocyanine compound thus prepared was dispersed in PMMA to prepare a PMMA dispersion film. The PMMA dispersion film was then subjected to spectroscopic evaluation. The spectroscopic evaluation of the PMMA dispersion film was performed using a JASCO V-770 ultraviolet-visible-near-infrared spectrophotometer connected to an ILF-533 integrating sphere. The measurement results are shown in FIG. 7. FIG. 7 also shows the spectral characteristics of 2,9,16,23-tetrakis(tert-butyl)phthalocyanine as a comparative example. The dispersion film of Example 1 exhibited almost no absorption or emission in the visible light wavelength range and was transparent in the visible light wavelength range. Visual observation revealed that the dispersion film of the phthalocyanine of the comparative example was blue, whereas the dispersion film of Example 1 was transparent.

[0077] Example 2 Example 2 differs from Example 1 in that a first phthalocyanine compound was evaluated. That is, the central element M of the phthalocyanine compound of Example 2 is two hydrogen atoms.

[0078] Example 2 was evaluated in the same manner as in Example 1. The phthalocyanine compound of Example 2 had an absorption spectrum with a peak wavelength of 896 nm and an emission spectrum with a peak wavelength of 972 nm.

[0079] Example 3 Example 3 differs from Example 1 in that the compound added in the substitution step during the preparation of the second phthalocyanine compound in Example 1 was changed. Specifically, zinc acetate dihydrate (9.2 mg, 50 μmol) was changed to manganese chloride anhydride (12.4 mg, 100 μmol). The other conditions were the same as in Example 1. The central element M of the phthalocyanine compound of Example 3 is Mn, and one Cl is coordinated as the axial ligand L.

[0080] Example 3 was evaluated in the same manner as in Example 1. The peak wavelength of the absorption spectrum of the phthalocyanine compound of Example 3 was 1019 nm.

[0081] Example 4 Example 4 differs from Example 1 in that the compound added in the substitution step during the preparation of the second phthalocyanine compound in Example 1 was changed. Specifically, zinc acetate dihydrate (15.6 mg, 71 μmol) was changed to tin(II) chloride (181.6 mg, 100 μmol). The other conditions were the same as those in Example 1. The central element M of the phthalocyanine compound of Example 4 is Sn, and two chlorine atoms are coordinated as the axial ligand L.

[0082] Example 4 was evaluated in the same manner as in Example 1. The peak wavelength of the absorption spectrum of the phthalocyanine compound of Example 4 was 1011 nm.

[0083] Example 5 Example 5 differs from Example 1 in that the compound added in the substitution step during the preparation of the second phthalocyanine compound in Example 1 was changed. Specifically, zinc acetate dihydrate (15.6 mg, 71 μmol) was changed to magnesium acetate (12.6 mg, 88 μmol). The other conditions were the same as in Example 1. The central element M of the phthalocyanine compound of Example 5 was Mg.

[0084] Example 5 was evaluated in the same manner as in Example 1. The phthalocyanine compound of Example 5 had an absorption spectrum with a peak wavelength of 834 nm and an emission spectrum with a peak wavelength of 917 nm.

[0085] Example 6 Example 6 differs from Example 1 in that the compound added in the substitution step during the preparation of the second phthalocyanine compound in Example 1 was changed. Specifically, zinc acetate dihydrate (15.6 mg, 71 μmol) was changed to copper (II) acetate (12.4 mg, 68 μmol). The other conditions were the same as in Example 1. The central element M of the phthalocyanine compound in Example 5 was Cu.

[0086] Example 6 was evaluated in the same manner as in Example 1. The peak wavelength of the absorption spectrum of the phthalocyanine compound of Example 6 was 860 nm.

[0087] Example 7 Example 7 differs from Example 1 in that p-anisidine was used instead of aniline when preparing the first precursor of Example 1, and a first phthalocyanine compound was prepared and evaluated. The phthalocyanine compound of Example 7 differs from the first phthalocyanine compound of Example 1 in that R1 is a p-methoxyphenyl group. That is, the phthalocyanine compound of Example 7 differs from Example 2 in that R1 is a p-methoxyphenyl group.

[0088] Example 7 was evaluated in the same manner as in Example 1. The phthalocyanine compound of Example 7 had an absorption spectrum with a peak wavelength of 935 nm and an emission spectrum with a peak wavelength of 1000 nm.

[0089] Example 8 Example 8 differs from Example 1 in that a first phthalocyanine compound was prepared and evaluated by using 3-aminopyridine instead of aniline when preparing the first precursor of Example 1. The phthalocyanine compound of Example 8 differs from the first phthalocyanine compound of Example 1 in that R1 is a 3-pyridyl group. That is, the phthalocyanine compound of Example 8 differs from Example 2 in that R1 is a 3-pyridyl group.

[0090] Example 8 was evaluated in the same manner as in Example 1. The phthalocyanine compound of Example 8 had an absorption spectrum with a peak wavelength of 868 nm and an emission spectrum with a peak wavelength of 977 nm.

[0091] Example 9 Example 9 differs from Example 1 in that a first phthalocyanine compound was prepared and evaluated using 4-chloroaniline instead of aniline when preparing the first precursor of Example 1. The phthalocyanine compound of Example 9 differs from the first phthalocyanine compound of Example 1 in that R1 is a p-chlorophenyl group. That is, the phthalocyanine compound of Example 9 differs from Example 2 in that R1 is a p-chlorophenyl group.

[0092] Example 9 was evaluated in the same manner as in Example 1. The phthalocyanine compound of Example 9 had an absorption spectrum with a peak wavelength of 898 nm and an emission spectrum with a peak wavelength of 987 nm.

[0093] Example 10 Example 10 differs from Example 1 in that a first phthalocyanine compound was prepared and evaluated by using 4-tert-butylaniline instead of aniline when preparing the first precursor of Example 1. The phthalocyanine compound of Example 10 differs from the first phthalocyanine compound of Example 1 in that R1 is a p-tert-butylphenyl group. That is, the phthalocyanine compound of Example 10 differs from Example 2 in that R1 is a p-tert-butylphenyl group.

[0094] Example 10 was evaluated in the same manner as in Example 1. The phthalocyanine compound of Example 10 had an absorption spectrum with a peak wavelength of 934 nm and an emission spectrum with a peak wavelength of 1017 nm.

[0095] Example 11 In Example 11, the second precursor obtained in Example 10 was used to prepare a phthalocyanine compound in which the central element M was Ni.

[0096] The second precursor (49.9 mg, 0.11 mmol) obtained in Example 10, nickel acetate (12.1 mg, 68 μmol), and 1,8-diazabicyclo[5.4.0]undecene-7 (0.3 mL) were dissolved in 1-hexanol (1 mL) and stirred at 150°C for 24 hours. The reaction solution was then cooled to room temperature, concentrated, and the resulting solid was washed with methanol to obtain a crude product. The crude product was then purified by alumina column chromatography (developing solvent: chloroform) to obtain 2.1 mg of a dark green solid. The yield was 4%.

[0097] Next, the molecular structure of the obtained dark green solid crystal was measured using NMR (nuclear magnetic resonance) under the following conditions. 500 MHz 1 H NMR (CDCl3) δ (ppm): 7.54 (s, 8H), 7.24-7.15 (m, 24H), 6.80-6.75 (m, 16H), 3.31 (s, 24H). UV-vis-NIR (THF) λ max nm (ε x 10-4 ): 896 (5.0), 800 (3.0), 483 (1.0), 337 (7.0).

[0098] As a result, it was confirmed that a phthalocyanine compound represented by chemical formula V in FIG. 8 was obtained.

[0099] Example 11 was evaluated in the same manner as in Example 1. The peak wavelength of the absorption spectrum of the phthalocyanine compound of Example 11 was 896 nm.

[0100] FIG. 9 shows a summary of the phthalocyanine compounds that were evaluated in each example. [Industrial Applicability]

[0101] The phthalocyanine compound of the present invention is applicable to, for example, photoelectric conversion elements, imaging elements, dye-sensitized solar cells, color filters, photothermal conversion materials, near-infrared photosensitizers, catalysts, and the like.

Claims

1. It is represented by the following formula (1): 【Chemical 1】 In the formula: M is any one selected from the group consisting of two hydrogen atoms, Zn, Mn, Sn, Mg, Cu, and Ni; R １ are each a phenyl group, a naphthyl group, a group having a nitrogen-containing heterocycle, or a group in which any of these is partially substituted, R ２ are each a hydrogen atom, an aryl group, an alkyl group having 6 or less carbon atoms, or a group in which any of these groups is partially substituted, R ３ and a photoelectric conversion film containing a phthalocyanine compound, each of which is hydrogen.

2. The photoelectric conversion film of claim 1, which is transparent to the visible light wavelength range of 350 nm to 780 nm.

3. A step of synthesizing a precursor represented by the following formula (2): 【Chemistry 2】 and reacting the precursor to synthesize a compound represented by the following chemical formula (1): 【Chemistry 3】 In the formula: M is two hydrogen atoms, a central element, or a central element coordinated with an axial ligand; R 1 is a phenyl group, a naphthyl group, a group having a nitrogen-containing heterocycle, or a group in which any of these is partially substituted; R 2 is hydrogen, an aryl group, an alkyl group having 6 or less carbon atoms, or a group in which any of these is partially substituted; The method for producing a phthalocyanine compound, wherein each R 3 is hydrogen.

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