Organic compound and electrochromic element

Abstract

To provide an organic compound with a more stable structure in the first reduced state.SOLUTION: The organic compound is represented by the general formula (1) in the figure. In the formula, X1 and X2 are each selected from among alkyl groups, aryl groups, and aralkyl groups; R1 to R8 are each selected from a hydrogen atom, a deuterium atom, halogen atoms, alkyl groups, alkoxy groups, and aryl groups; and R11 to R14 are each selected from a hydrogen atom, alkyl groups, and aryl groups.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an organic compound and an electrochromic device using the same.

Background Art

[0002] An electrochromic (hereinafter sometimes referred to as "EC") device is a device having a pair of electrodes and an EC layer between the pair of electrodes. By applying a voltage to the pair of electrodes, the amount of light passing through the EC layer can be adjusted. In other words, an EC device is a device capable of controlling the light transmittance.

[0003] An EC material is a material whose optical absorption properties (such as coloring state and light transmittance) change by an electrochemical oxidation-reduction reaction. As EC materials, various materials such as inorganic materials, organic low-molecular materials, and polymer materials are known.

[0004] Using these materials, EC devices have been applied to dimming mirrors for automobiles, electronic paper, and the like. These devices utilize the characteristic that various color tones can be displayed by selecting materials. In utilizing EC devices, it is necessary to develop materials with various color tones. For example, when considering application to a full-color display or the like, materials that color cyan, magenta, and yellow are required. When considering application to a wider range of uses, coloring materials with various color tones are required.

[0005] Patent Document 1 discloses Compound 1-a, which is a cathodic EC compound.

[0006]

Chemical Formula

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, the compound described in Patent Document 1 has room for improvement in the stability of the compound in the first reduced state.

[0009] The present invention has been made in view of the above problems, and an object thereof is to provide an organic compound in which the wavelength of light that can be absorbed is more stable.

MEANS FOR SOLVING THE PROBLEMS

[0010] The organic compound according to the present invention is characterized by being represented by the general formula (1).

[0011]

CHEMICAL FORMULA

[0012] In the general formula (1), X1 and X2 are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group.

[0013] R1 to R8 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group.

[0014] R 11 to R 14 are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

EFFECTS OF THE INVENTION

[0015] According to the present invention, it is possible to provide an organic compound in which the wavelength of light that can be absorbed is more stable.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Mode for Carrying Out the Invention

[0017] In the present specification, examples of the halogen atom include, but are not limited to, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0018] The alkyl group may be an alkyl group having 1 to 20 carbon atoms, may be an alkyl group having 1 to 12 carbon atoms, or may be an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. For example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tert-butyl group, a secondary butyl group, an octyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, etc. may be mentioned, but it is not limited thereto. Further, examples of the substituent that the alkyl group may have include a halogen atom, an ester group, and a cyano group, but it is not limited thereto. Further, a hydrogen atom in the alkyl group may be substituted with a halogen atom, preferably a fluorine atom. Further, a carbon atom of the alkyl group may be substituted with an ester group or a cyano group.

[0019] The aryl group may be an aryl group having 6 to 20 carbon atoms, or may be an aryl group having 6 to 10 carbon atoms. For example, a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a triphenylenyl group, a perylenyl group, etc. may be mentioned, but it is not limited thereto. The aryl group may have at least one of a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms as a substituent. A hydrogen atom in the alkyl group or the alkoxy group may be substituted with a halogen atom, preferably a fluorine atom.

[0020] The alkoxy group may be an alkoxy group having 1 to 10 carbon atoms, or may be an alkoxy group having 1 to 4 carbon atoms. For example, a methoxy group, an ethoxy group, a propoxy group, an iso-propoxy group, a butoxy group, a tert-butoxy group, a 2-ethyl-octyloxy group, a benzyloxy group, etc. may be mentioned, but it is not limited thereto.

[0021] Examples of the aryloxy group include, but are not limited to, a phenoxy group.

[0022] The aralkyl group may be an aralkyl group having 7 to 20 carbon atoms, or may be an aralkyl group having 7 to 10 carbon atoms. Examples include, but are not limited to, a benzyl group and a phenethyl group. The aralkyl group may have a substituent, specifically, it may have an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. The hydrogen atom in the alkyl group or alkoxy group may be substituted with a halogen atom, preferably a fluorine atom.

[0023] Examples of the ester group include, but are not limited to, a carboxylic acid ester group, a sulfonic acid ester group, and a phosphonic acid ester group.

[0024] In this specification, the cathodic EC compound refers to an organic compound that colors upon reduction. The anodic EC compound refers to an organic compound that colors upon oxidation.

[0025] In this specification, "coloring" means that the transmittance at a specific wavelength decreases. The organic compound that colors upon reduction refers to an organic compound in which the transmittance of visible light during reduction is lower than the transmittance of visible light during oxidation. The organic compound that colors upon oxidation refers to an organic compound in which the transmittance of visible light during oxidation is lower than the transmittance of visible light during reduction. It is sufficient that the transmittance changes in any part of the visible light region, and it is not necessary for the transmittance to change throughout the entire visible light region.

[0026] (1) Organic compound First, the organic compound according to the present invention will be described.

[0027] The organic compound according to the present invention is an organic compound represented by the following general formula (1) and has EC properties. Therefore, the organic compound according to the present invention can be called an EC compound. Further, the organic compound according to the present invention is an organic compound that colors upon reduction.

[0028]

Chemical formula

[0029] In general formula (1), X1 and X2 are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group.

[0030] X1 and X2 may be an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, may be an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, may be a heptyl group or a phenyl group, and may be a heptyl group.

[0031] X1 and X2 may have the same structure or different structures. From the viewpoint of ease of synthesis, X1 and X2 preferably have the same structure.

[0032] When X1 and X2 are alkyl groups, they may have an adsorption group for adsorbing to an electrode or an acid ester group thereof. The electrode is preferably a porous electrode. Specific examples of the adsorption group and the acid ester group thereof include a carboxyl group and a carboxylic acid ester group, a sulfonic acid group and a sulfonic acid ester group, a phosphonic acid group and a phosphonic acid ester group, a trialkoxysilyl group, and the like. When X1 and X2 have an adsorption group and an acid ester group thereof, X1 and X2 may have a carboxyl group, a carboxylic acid ester group, a sulfonic acid group, a phosphonic acid group, or a phosphonic acid ester group, and may have a carboxyl group, a sulfonic acid group, a phosphonic acid group, or a phosphonic acid ester group.

[0033] In addition, the terminal of the alkyl group may have a polymerizable functional group in order to polymerize the compound of the present invention. Specific examples of the polymerizable functional group include an acrylic group, a methacrylic group, a hydroxyl group, and the like. Further, in order to improve the solubility in an organic solvent, the terminal of the alkyl group may have an ionic group such as a pyridinium group or a quinolinium group.

[0034] When X1 and X2 are aralkyl groups and aryl groups and have an alkyl group or an alkoxy group as a substituent, the terminal thereof may have an adsorption group for adsorbing to an electrode or an acid ester group thereof, and may also have a polymerizable functional group for polymerization. It may have an ionic group to improve the solubility in an organic solvent. Specific examples of the adsorption group, the acid ester group thereof, and the ionic group are the same as the examples described above. When X1 and X2 have an adsorption group, an acid ester group thereof, and an ionic group, X1 and X2 may have a carboxyl group, a carboxylic acid ester group, a sulfonic acid group, a phosphonic acid group, a phosphonic acid ester group, or a pyridinium group, and may have a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphonic acid ester group, or a pyridinium group.

[0035] R1 to R8 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group.

[0036] R1 to R8 may be a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, may be a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, a methoxy group, or a phenyl group, may be a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, or a phenyl group, and may be a hydrogen atom.

[0037] R 11 to R 14 is each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

[0038] R 11 to R 14 may be a hydrogen atom, a deuterium atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, may be a hydrogen atom, a deuterium atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and may be a hydrogen atom or a methyl group.

[0039] Further, the organic compound according to the present embodiment may have monovalent anions A1 - and A2 - as counterions. A1 - and A2 - are selected from anions such as PF6 - , ClO4 - , BF4 - , AsF6 - , SbF6 - , CF3SO3 - , (CF3SO2)2N - and the like, and halogen anions such as Br - , Cl - , I - each independently. A1 - and A2 - are Cl - , Br - , I - , BF4 - , PF6 -, ClO4 - , CF3SO3 - or (CF3SO2)2N - may be.

[0040] A1 - and A2 - may have different structures or the same structure, but from the viewpoint of ease of synthesis, it is preferably the same structure.

[0041] In other words, the organic compound represented by the general formula (1) may be represented by the general formula (2).

[0042]

Chemical formula

[0043] In the general formula (2), R1 to R8, R 11 to R 14 , X1 and X2, are A1 - and A2 - have the same structure as that shown in the general formula (1).

[0044] The organic compound represented by the general formula (1) has the following characteristics. (1-1) Having a stable structure in the first reduced state (1-2) Since it consists of a condensed ring skeleton, it has excellent durability

[0045] Hereinafter, these characteristics will be described.

[0046] (1-1) Having a stable structure in the first reduced state Since the organic compound according to the present invention is represented by the general formula (1), it has a more stable structure in the first reduced state compared to the organic compound described in Patent Document 1. Specifically, the difference between the first reduction potential and the second reduction potential of the organic compound according to the present invention is larger than the difference between the first reduction potential and the second reduction potential of the organic compound described in Patent Document 1.

[0047] Here, the effect due to a large difference between the first reduction potential and the second reduction potential will be described. The EC compound performs coloring and extinction by changing the absorption wavelength through a redox reaction. The absorption wavelength of the EC compound in the first reduced state (one-electron reduced state) and the absorption wavelength in the second reduced state (two-electron reduced state) may be different. At this time, if the difference between the first reduction potential and the second reduction potential is small, due to local potential changes, etc., the possibility of the coexistence of the first reduced state and the second reduced state in the system becomes high. As a result, the EC compound is likely to absorb light of an unintended wavelength, and thus the wavelength of light that the EC compound can absorb tends to be unstable. On the other hand, if the difference between the first reduction potential and the second reduction potential is large, the coexistence of the first reduced state and the second reduced state in the system becomes difficult. As a result, the wavelength of light that the EC compound can absorb becomes more stable. Therefore, it is preferable that the difference between the first reduction potential and the second reduction potential is large. Specifically, the difference between the first reduction potential and the second reduction potential is preferably greater than 0.12V, more preferably 0.15V or more, still more preferably 0.17V or more, and particularly preferably 0.20V or more.

[0048] The difference between the first reduction potential and the second reduction potential can be determined by cyclic voltammetry (CV) measurement or the like. Specifically, a solvent, an electrolyte having a concentration of 0.1 mol / L with respect to the solvent, and an EC compound having a concentration of 0.5 mmol / L with respect to the solvent are dissolved to obtain a solution. CV measurement is performed on the solution using a three-electrode cell having a working electrode, a counter electrode, and a reference electrode, and taking ferrocene as a reference substance, with E 1 / 2 set to 0V, the reduction potential with the largest value among the plurality of reduction peaks of the obtained EC compound is taken as the first reduction potential, and the reduction potential with the second largest value after the first reduction potential is taken as the second reduction potential, whereby the difference between the first reduction potential and the second reduction potential can be determined. Here, E 1 / 2 is a value called the half-wave potential. Specifically, it is the potential that is the midpoint between the oxidation potential and the re-reduction potential, or the potential that is the midpoint between the reduction potential and the re-oxidation potential. Also, the reduction potential is usually represented by a negative value. Therefore, "a large reduction potential" means that the absolute value of the reduction potential is small.

[0049] Since the difference between the first reduction potential and the second reduction potential of the organic compound according to the present invention is larger than the difference between the first reduction potential and the second reduction potential of the organic compound described in Patent Document 1, it is preferable because the EC compound is less likely to absorb light of an unintended wavelength. Further, since the difference between the first reduction potential and the second reduction potential of the organic compound according to the present invention is 0.12 V or more, the EC compound is less likely to absorb light of an unintended wavelength, which is more preferable.

[0050] (1-2) Since it consists of a condensed ring skeleton, it has excellent durability Since the organic compound according to the present invention consists of a condensed ring skeleton, it has excellent durability compared to Compound 1-a.

[0051] It is considered that the radical cation of the π-conjugated molecule undergoes planarization of the π-conjugated portion due to resonance stabilization of the radical. Since Compound 1-a has a skeleton in which an azafluorene ring and a pyridine ring are bonded by a single bond, the structural change before and after the redox reaction tends to be large. On the other hand, since the organic compound according to the present invention forms a condensed ring skeleton and the π-conjugated portion is planar in the ground state, the structural change of the compound due to the redox reaction is small. In other words, since the structural change before and after the redox reaction is likely to be small, the decomposition of the compound due to the redox reaction can be reduced. As a result, the organic compound according to the present invention is an organic compound having excellent durability.

[0052] Furthermore, the organic compound according to the present invention may have the following characteristics.

[0053] (1-3) Having a substituent that improves solubility in a solvent As will be described later, the organic compound according to the present invention may be used after being dissolved in a solvent. Therefore, it is preferable that the organic compound according to the present invention has a substituent that improves solubility in a solvent.

[0054] In order to improve the solubility of the organic compound according to the present invention in a solvent, the organic compound according to the present invention preferably has a bulky substituent. Examples of the bulky substituent include an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. Specifically, it may be an iso-propyl group, a tert-butyl group, a methoxy group, an ethoxy group, an iso-propoxy group, a tert-butoxy group, a ter-phenyl group, or a phenoxy group.

[0055] When the organic compound according to the present invention is dissolved in a polar solvent and used, it is preferable to provide a substituent that increases the polarity of the organic compound according to the present invention. For example, an alkoxy group having 1 to 7 carbon atoms or an aryloxy group having 6 to 10 carbon atoms can be mentioned. Specifically, it may be a methoxy group, an ethoxy group, an iso-propoxy group, a tert-butoxy group, or a phenoxy group. Since the organic compound according to the present invention has these substituents and thus has increased polarity, the solubility in a polar solvent is further improved.

[0056] Hereinafter, a method for producing the organic compound according to the present invention will be described.

[0057] There is no particular limitation on the method for producing the organic compound according to the present invention. For example, it can be produced by the method shown below. When at least one of X1 and X2 is an alkyl group or an aralkyl group, the organic compound represented by the following general formula (3) is reacted with a halide in a predetermined solvent. Then, it can be obtained by performing an anion exchange reaction with a salt containing a desired anion in a predetermined solvent.

[0058]

Chemical formula

[0059] When at least one of X1 and X2 is an aryl group, it is reacted with an organic compound represented by the following general formula (3) and a hypervalent iodine compound. Then, it can be obtained by subjecting a salt containing an anion to an anion exchange reaction in a predetermined solvent. Also, by selecting the solvent and the reaction temperature, only one imine on one side can be reacted. By repeating the reaction, it is also possible to introduce different substituents into the two imines.

[0060] The method for producing the organic compound represented by the above general formula (3) is not particularly limited, but for example, it can be produced according to the production method shown below. R1 to R8, R 11 to R 14 represent a hydrogen atom or a substituent in the same manner as in the general formula (1).

[0061]

Chemical formula

[0062] Intermediate 1 can be synthesized by methylating 4-nicotinic acid derivative with a methylating agent. Intermediate 2 can be synthesized by coupling Intermediate 1 with a phenylenediboronic acid derivative. Also, an asymmetric molecule can be synthesized by sequentially reacting different Intermediate 1 with a phenyldiboronic acid derivative. Intermediate 3 can be synthesized by reacting Intermediate 2 with a Grignard reagent. The organic compound represented by the general formula (3) can be synthesized by subjecting Intermediate 3 to a cyclization reaction in the presence of an acid.

[0063] Hereinafter, specific structural formulas of the organic compounds according to the present invention are shown. However, the compounds according to the present invention are not limited thereto.

[0064]

Chemical formula

[0065]

Chemical formula

[0066]

Chem.

[0067]

Chem.

[0068] Among the above-exemplified compounds, the compounds in which X1 and X2 have the same structure are compounds that are easy to synthesize. Specifically, they are A-1 to A-20, A-25 to A-41.

[0069] Among the above-exemplified compounds, the compounds in which X1 and X2 have an alkyl group are compounds with excellent durability. Specifically, they are A-1 to A-12, A-21 to A-35, A-38 to A-39.

[0070] Among the above-exemplified compounds, the compounds in which X1 and X2 have an aryl group are compounds in which the absorption wavelength can be easily adjusted. Specifically, they are A-13 to A-23, A-21 to A-24.

[0071] All of the above-exemplified compounds are organic compounds having a more stable structure in the first reduced state because they are represented by the general formula (1).

[0072] ≪EC Element≫ The organic compound according to the present invention can be used for the EC layer of an EC element. Hereinafter, the EC element according to the present embodiment will be described with reference to the drawings.

[0073] The EC element 1 in FIG. 1 has a pair of electrodes 11 and an EC layer 12 disposed between the pair of electrodes. The EC element 1 may further have a pair of transparent substrates 10. Further, the EC element 1 may further have a spacer 13, and the pair of electrodes 11 have a constant inter-electrode distance by the spacer 13.

[0074] The EC layer 12 contains the organic compound according to the present invention. This EC layer 12 may have a layer composed of the organic compound according to the present invention and a layer composed of an electrolyte. Alternatively, the EC layer 12 may be provided as a solution containing an EC compound and an electrolyte. When the EC layer 12 is a solution layer, the organic compound according to the present invention, the solution, and other dissolved substances may be collectively referred to as an EC medium.

[0075] Hereinafter, the components of the EC element 1 according to the present embodiment will be described.

[0076] <Substrate 10> As the substrate 10, for example, colorless or colored glass, tempered glass, etc. are used, and colorless or colored transparent resins are also used. The substrate 10 is preferably a transparent substrate. In the present embodiment, the transparent substrate refers to a substrate having a visible light transmittance of 90% or more. Specifically, polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, etc. may be mentioned.

[0077] <Electrode 11> Examples of the material of the electrode 11 include metals and metal oxides such as indium tin oxide alloy (ITO), fluorine-doped tin oxide (FTO), tin oxide (NESA), indium zinc oxide (IZO), silver oxide, vanadium oxide, molybdenum oxide, gold, silver, platinum, copper, indium, chromium, etc., silicon-based materials such as polycrystalline silicon and amorphous silicon, and carbon materials such as carbon black, graphite, and glassy carbon. The electrode 11 is preferably a transparent electrode. In the present embodiment, the transparent electrode refers to a substrate having a visible light transmittance of 90% or more.

[0078] In addition, conductive polymers with improved conductivity through doping treatment or the like, such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, a complex of polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid, etc. are also preferably used.

[0079] Furthermore, the electrode 11 may be a porous electrode. The porous electrode preferably has a porous shape, a lot shape, a wire shape, etc. with fine pores on the surface and inside, and a material with a large surface area. As the material of the porous electrode, for example, metals, metal oxides, carbon, etc. can be applied. More preferably, metal oxides such as titanium oxide, tin oxide, iron oxide, strontium oxide, tungsten oxide, zinc oxide, tantalum oxide, vanadium oxide, indium oxide, nickel oxide, manganese oxide, cobalt oxide, etc.

[0080] <EC layer 12> Examples of the electrolyte include the following. When the electrolyte is a liquid electrolyte, the electrolyte has an ion-dissociable salt. The ion-dissociable salt is not particularly limited as long as it is a compound that shows good solubility in the solvent. When the electrolyte is a solid electrolyte, it is not particularly limited as long as it shows high compatibility with the organic compound according to the present invention. Among them, an electrolyte having an electron-donating property is preferable. These electrolytes can also be called supporting electrolytes. Examples of the electrolyte include various inorganic ion salts such as various alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, and cyclic quaternary ammonium salts. Specifically, alkali metal salts of Li, Na, K such as LiClO4, LiSCN, LiBF4, LiAsF6, LiCF3SO3, LiPF6, LiI, NaI, NaSCN, NaClO4, NaBF4, NaAsF6, KSCN, KCl, etc., and quaternary ammonium salts and cyclic quaternary ammonium salts such as (CH3)4NBF4, (C2H5)4NBF4, (n-C4H9)4NBF4, (n-C4H9)4NPF6, (C2H5)4NBr, (C2H5)4NClO4, (n-C4H9)4NClO4, etc.

[0081] As for the solvent that dissolves the organic compound and electrolyte according to the present invention, there is no particular limitation as long as it can dissolve them, but those having polarity are particularly preferred. Specifically, water, and organic polar solvents such as methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, propionitrile, benzonitrile, dimethylacetamide, N-methylpyrrolidinone, dioxolane, etc. can be mentioned.

[0082] For the EC layer 12, it is also possible to use those having high viscosity by further containing a polymer or a gelling agent, or those in a gel state, etc.

[0083] These polymers and gelling agents can also be called thickeners. By having a thickener, the viscosity of the EC solution can be increased. Since the movement of molecules in the EC solution can be suppressed by the high viscosity of the EC solution, the organic compound according to the present invention is less likely to form an aggregate, and the temperature dependence of the absorption spectrum can be reduced. Therefore, it is preferable for the EC solution to have a thickener.

[0084] On the other hand, when the viscosity of the EC solution is too high, the movement of molecules in the EC solution is suppressed, so the reaction rate of the EC element becomes small. Therefore, it is not preferable for the viscosity of the EC solution to be too high.

[0085] Specifically, the viscosity of the EC solution may be 10 cP or more and 5000 cP or less, and may be 50 cP or more and 1000 cP or less. The viscosity of the EC solution may be 150 cP or less, preferably 100 cP or less, more preferably 65 cP or less. Also, the viscosity of the EC solution may be 20 cP or more, preferably 50 cP or more.

[0086] When the weight of the entire EC solution is 100 wt%, the thickener may have a weight ratio of 20 wt% or less. Preferably, it is 1 wt% or more and 15 wt% or less, and more preferably, 5 wt% or more and 10 wt% or less.

[0087] The polymer is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethyl cellulose, polyvinyl chloride, polyalkylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, Nafion (registered trademark), and the like. Polymethyl methacrylate, polyethylene oxide, and polypropylene oxide are preferable.

[0088] The EC element according to the present embodiment may have an organic compound according to the present invention and an organic compound (first organic compound) different from the organic compound according to the present invention. The first organic compound may be one kind or a plurality of kinds, and may be a compound that colors in an oxidized state, a compound that colors in a reduced state, or a compound having both properties. Since the organic compound having a skeleton represented by the general formula (1) is a compound that colors in a reduced state, the first organic compound is preferably a compound that colors in an oxidized state.

[0089] The organic compound according to the present invention can absorb a desired color as an EC element by combining with coloring materials of other colors. The other organic compound during coloring preferably has an absorption wavelength in the range of 400 nm or more and 800 nm or less, and more preferably, has an absorption wavelength in the range of 420 nm or more and 700 nm or less. Having an absorption wavelength in a specific range means that the peak of the absorption spectrum may be in a specific range. By combining a plurality of the organic compound according to the present invention and the first organic compound, it is also possible to produce an EC element that absorbs all of the visible region and colors black.

[0090] The EC element according to the present embodiment preferably has four or more types of EC compounds together with the organic compound according to the present invention. This is because a filter having an EC element is likely to uniformly absorb light of each wavelength.

[0091] As the first organic compound according to this embodiment, for example, a compound having the following structural formula can be mentioned.

[0092] Examples of the first organic compound that colors upon oxidation include oligothiophene-based compounds, phenazine-based compounds such as 5,10-dihydro-5,10-dimethylphenazine and 5,10-dihydro-5,10-diisopropylphenazine, metallocene-based compounds such as ferrocene, tetra-t-butylferrocene, and titanocene, phenylenediamine-based compounds such as N,N',N,N'-tetramethyl-p-phenylenediamine, and pyrazolone-based compounds such as 1-phenyl-2-pyrazoline.

[0093] Examples of the first organic compound that colors upon reduction include viologen-based compounds such as N,N'-diheptylbipyridinium diperchlorate, N,N'-diheptylbipyridinium ditetrafluoroborate, N,N'-diheptylbipyridinium dihexafluorophosphate, N,N'-diethylbipyridinium diperchlorate, N,N'-diethylbipyridinium ditetrafluoroborate, N,N'-diethylbipyridinium dihexafluorophosphate, N,N'-dibenzylbipyridinium diperchlorate, N,N'-dibenzylbipyridinium ditetrafluoroborate, N,N'-dibenzylbipyridinium dihexafluorophosphate, N,N'-diphenylbipyridinium diperchlorate, N,N'-diphenylbipyridinium ditetrafluoroborate, and N,N'-diphenylbipyridinium dihexafluorophosphate, anthraquinone-based compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, and octamethylanthraquinone, ferrocenium salt-based compounds such as ferrocenium tetrafluoroborate and ferrocenium hexafluorophosphate, and styrylated compounds.

[0094] In this embodiment, the phenazine-based compound is a compound containing a 5,10-dihydrophenazine skeleton in its chemical structure, and also includes compounds having a substituent on 5,10-dihydrophenazine. For example, the hydrogen atoms at the 5- and 10-positions of 5,10-dihydrophenazine may be substituted with an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms. Specifically, it may be an alkyl group such as a methyl group, an ethyl group, a propyl group, an iso-propyl group, a normal butyl group, a tert-butyl group, or an aryl group such as a phenyl group or a naphthyl group.

[0095] Further, the phenazine-based compound may have a substituent on the 5,10-dihydrophenazine skeleton. Examples of the substituent that the 5,10-dihydrophenazine skeleton may have include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. Specifically, it may be an alkyl group such as a methyl group, an ethyl group, a propyl group, a normal butyl group, a tert-butyl group, an aryl group such as a phenyl group or a naphthyl group, or an aryloxy group such as a phenoxy group.

[0096] Moreover, the substituent that the 5,10-dihydrophenazine skeleton has may further have a substituent, and it may be an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Specifically, it may be an alkyl group such as a methyl group, an ethyl group, a propyl group, a normal butyl group, a tert-butyl group, or an alkoxy group such as a methoxy group or an iso-propoxy group.

[0097] The same applies to the substituents of other compounds, such as viologen-based compounds.

[0098] As the first organic compound, among the above, it is preferably any one of a phenazine-based compound, a metallocene-based compound, a phenylenediamine-based compound, and a pyrazoline-based compound.

[0099] The compound contained in the EC layer of the EC element according to this embodiment can be confirmed to be contained in the EC element by extracting and analyzing it by a known method. For example, extraction by chromatography and analysis by NMR can be mentioned. Further, when the electrochromic layer is solid, it can be analyzed by TOF-SIMS or the like.

[0100] <Spacer 13> Spacer 13 is disposed between a pair of electrodes 11 and provides a space for accommodating the EC layer 12. Specifically, polyimide, polytetrafluoroethylene, fluororubber, epoxy resin, etc. can be used. By this spacer 13, it is possible to maintain the inter-electrode distance of the EC element 1.

[0101] The EC element according to this embodiment may have a liquid injection port formed by a pair of electrodes 11 and a spacer 13. After enclosing the composition containing the organic compound according to the present invention from the liquid injection port, the liquid injection port is covered with a sealing member and further sealed with an adhesive or the like to obtain the EC element 1. The sealing member also serves to isolate the adhesive and the composition so that they do not come into contact. The shape of the sealing member is not particularly limited, but a tapered shape such as a wedge shape is preferable.

[0102] The method for forming the EC element according to this embodiment is not particularly limited, and a method of injecting a liquid containing an EC compound prepared in advance by a vacuum injection method, an air injection method, a meniscus method, or the like into a gap provided between a pair of electrodes 11 can be used.

[0103] ≪Use of EC element≫ By driving the EC element according to this embodiment, the amount of light passing through the EC element can be adjusted. The EC element according to this embodiment can be used for an optical filter, a lens unit, an imaging device, a window material, etc.

[0104] <Optical filter> The optical filter according to this embodiment has an EC element 1 and an active element connected to the EC element 1. The optical filter according to this embodiment may include a peripheral device. The active element may be directly connected to the EC element 1 or indirectly connected via another element. The active element drives the EC element 1 and adjusts the amount of light passing through the EC element. Examples of the active element include a transistor and the like. The transistor may have an oxide semiconductor such as InGaZnO in the active region.

[0105] The optical filter according to this embodiment has an EC element according to this embodiment and a driving device connected to the EC element according to this embodiment. FIG. 2 is a schematic diagram showing an example of a driving device 20 and an EC element 1 driven by the driving device 20. In this embodiment, the driving device 20 further includes a controller 7, a driving power source 8, and a resistance switcher 9.

[0106] The driving power source 8 applies a voltage (hereinafter sometimes referred to as "driving voltage") necessary for the EC compound contained in the EC layer 12 to cause an electrochemical reaction to the EC element 1. The driving voltage is more preferably a constant voltage. This is because when the EC layer 12 contains a plurality of types of EC compounds, the absorption spectrum may change due to the difference in the redox potential difference and molar extinction coefficient of each EC compound. The start of voltage application or the holding of the voltage application state of the driving voltage is performed by a signal from the controller 7. In this embodiment, the application state of a constant voltage is held during the period of controlling the light transmittance of the EC element 1.

[0107] The method for controlling the transmittance of the EC element 1 by the controller 7 adopts a method suitable for the EC element 1 used. Specifically, methods include inputting pre-specified conditions to the EC element 1 with respect to the set value of the desired transmittance, and comparing the set value of the transmittance with the transmittance of the EC element 1, then selecting and inputting conditions to match the set value. Examples of the parameter to be changed include voltage, current, and duty ratio. In this specification, the duty ratio refers to the ratio of the applied period of the applied voltage to one cycle of the pulse voltage waveform. The controller 7 can change the coloring density of the EC element 1 by changing the voltage, current, or duty ratio.

[0108] In this embodiment, known means can be used for voltage change, current change, and pulse width modulation. Also, pulse width modulation can be performed as follows.

[0109] The resistance switch 9 switches and serially connects a resistance R1 (not shown) and a resistance R2 larger than the resistance R1 in a closed circuit including the drive power supply 8 and the EC element 1. The resistance value of the resistance R1 is preferably at least smaller than the largest impedance of the element closed circuit, preferably 10 Ω or less. The resistance value of the resistance R2 is preferably larger than the largest impedance of the element closed circuit, preferably 1 MΩ or more. Note that the resistance R2 may be air. In this case, strictly speaking, the closed circuit becomes an open circuit, but it can be considered a closed circuit by regarding air as the resistance R2.

[0110] The controller 7 sends a switching signal to the resistance switch 9 to control the switching between the resistance R1 and the resistance R2. When the resistance is R1, the EC element 1 colors, and when the resistance is R2, the EC element 1 fades. During the period of the resistance R2, the EC compound self-fades. This self-fading is caused by the instability of the radical species of the EC compound generated during coloring, diffusion to the counter electrode having different potentials, and collisions in the solution between anodic radical species and cathodic radical species.

[0111] <Lens unit> The lens unit according to this embodiment includes an imaging optical system and an optical filter having an EC element according to this embodiment. The imaging optical system may have lenses, and the number of lenses may be one or plural. The optical filter may be provided either between a plurality of lenses or outside the lenses. Preferably, the optical filter is provided on the optical axis of the lens.

[0112] <Imaging device> The imaging device of this embodiment includes an optical filter having an EC element according to this embodiment and a light receiving element that receives light that has passed through the optical filter. Specifically, examples of the imaging device include a camera, a video camera, and a mobile phone with a camera. The imaging device may be configured such that a main body having a light receiving element and a lens unit having a lens can be separated. Here, when the imaging device can be separated into a main body and a lens unit, a form in which an optical filter separate from the imaging device is used during imaging is also included in the present invention. At this time, examples of the arrangement position of the optical filter include outside the lens unit, between the lens unit and the light receiving element, and between a plurality of lenses (when the lens unit has a plurality of lenses).

[0113] FIG. 3(a) is a schematic diagram of an example of an imaging device in which an optical filter is arranged in a lens unit, and FIG. 3(b) is a schematic diagram of an example of an imaging device in which an optical filter is arranged in an imaging device.

[0114] The imaging device 100 is an imaging device including a lens unit 102 and an imaging unit 103. The lens unit 102 includes an optical filter 101 and an imaging optical system having lenses. The optical filter 101 is the optical filter according to the above-described embodiment. The number of lenses may be one or a lens group composed of a plurality of lenses.

[0115] The lens unit 102 may be, for example, a rear focus type zoom lens that performs focusing behind the aperture. The lens unit 102 has four lens groups, namely, a first lens group 104 with a positive refractive power, a second lens group 105 with a negative refractive power, a third lens group 106 with a positive refractive power, and a fourth lens group 107 with a positive refractive power, in order from the subject (object) side. In the present embodiment, for example, zooming may be performed by changing the distance between the second lens group 105 and the third lens group 106, and focusing may be performed by moving a part of the fourth lens group 107.

[0116] The lens unit 102 may have, for example, an aperture stop 108 between the second lens group 105 and the third lens group 106, and may also have an optical filter 101 between the third lens group 106 and the fourth lens group 107. The light passing through the lens unit 102 is arranged to pass through each lens group 104 to 107, the aperture stop 108, and the optical filter 101, and the amount of light can be adjusted using the aperture stop 108 and the optical filter 101.

[0117] The lens unit 102 may be detachably connected to the imaging unit 103 via a mount member (not shown).

[0118] In the present embodiment, the optical filter 101 is disposed between the third lens group 106 and the fourth lens group 107 within the lens unit 102. However, the imaging device 100 is not limited to this configuration. For example, the optical filter 101 may be located either in front (subject side) or behind (imaging unit 103 side) of the aperture stop 108, or may be located in front of, behind, or between any of the first to fourth lens groups 104 to 107. Note that if the optical filter 101 is disposed at a position where light converges, there are advantages such as being able to reduce the area of the optical filter 101.

[0119] Moreover, the configuration of the lens unit 102 is not limited to the above-described configuration and can be appropriately selected. For example, in addition to the rear focus type, an inner focus type that performs focusing in front of the aperture may be used, or other types may be used. In addition to zoom lenses, special lenses such as fish-eye lenses and macro lenses can also be appropriately selected.

[0120] The imaging unit 103 includes a glass block 109 and a light receiving element 110. The glass block 109 is a glass block such as a low-pass filter, a face plate, or a color filter. The light receiving element 110 is a sensor unit that receives the light that has passed through the lens unit, and an imaging element such as a CCD or a CMOS can be used. Further, a light sensor such as a photodiode may be used, and those that acquire and output information on the intensity or wavelength of light can be appropriately used.

[0121] As shown in Fig. 3(a), when the optical filter 101 is incorporated in the lens unit 102, the driving device 20 may be arranged inside the lens unit 102 or outside the lens unit 102. When it is arranged outside the lens unit 102, the EC element 1 inside the lens unit 102 and the driving device 20 are connected through wiring for drive control.

[0122] In the configuration of the imaging device 100 described above, the optical filter 101 is arranged inside the lens unit 102. However, the present invention is not limited to this form, and the optical filter 101 may be arranged at an appropriate location inside the imaging device 100, and the light receiving element 110 may be arranged to receive the light that has passed through the optical filter 101.

[0123] For example, as shown in FIG. 3(b), the imaging unit 103 may have an optical filter 101. FIG. 3(b) is a diagram for explaining another example of the configuration of the imaging device according to the present embodiment, and is a schematic diagram of the configuration of an imaging device having an optical filter in the imaging unit 103. In FIG. 3(b), for example, the optical filter 101 is disposed immediately before the light receiving element 110. When the imaging device itself incorporates the optical filter 101, the connected lens unit 102 itself does not have to have the optical filter 101, so that it is possible to configure a dimming-capable imaging device using the existing lens unit 102.

[0124] The imaging device 100 according to the present embodiment is applicable to products having a combination of light amount adjustment and a light receiving element. For example, it can be used in cameras, digital cameras, video cameras, digital video cameras, and can also be applied to products incorporating an imaging device such as mobile phones, smartphones, PCs, and tablets.

[0125] According to the imaging device 100 according to the present embodiment, by using the optical filter 101 as a dimming member, it is possible to appropriately vary the dimming amount with a single filter, and there are advantages such as reduction in the number of components and space saving.

[0126] <Window> The window according to the present embodiment includes a pair of substrates, an EC element according to the present embodiment disposed between the pair of substrates, and an active element connected to the EC element according to the present embodiment. As a driving means for driving the EC element 1, an example of a method for adjusting the light amount of light passing through the EC element 1 by an active element connected to the EC element 1 can be mentioned, but it is not limited thereto. Examples of the active element include a transistor and the like. The transistor may have an oxide semiconductor such as InGaZnO in the active region. The window according to the present embodiment can also be called a variable transmittance window.

[0127] FIG. 4(a) is a schematic view showing a dimming window 111 as a window material using an EC element according to this embodiment, and FIG. 4(b) is a schematic view showing a cross-sectional view taken along line X-X' of FIG. 4(a). The dimming window according to this embodiment includes an EC element 1 (optical filter), transparent plates 113 sandwiching the EC element 1, and a housing 112. The EC element 1 has a driving device (not shown). The driving device may be integrated within the frame 112, or may be disposed outside the frame 112 and connected to the EC element 1 through wiring.

[0128] The material of the housing 112 is not particularly limited, and any material that covers at least a part of the EC element 1 and has an integrated form may be regarded as a frame. In FIG. 4(b), the EC element 1 is a component independent of the transparent plate 113. However, for example, the substrate 10 of the EC element 1 may be regarded as the transparent plate 113.

[0129] The transparent plate 113 is not particularly limited as long as it is a material with a high light transmittance, and is preferably a glass material in consideration of its use as a window.

[0130] The dimming window according to this embodiment can be applied, for example, to applications for adjusting the amount of sunlight entering a room during the day. In addition to adjusting the amount of sunlight, it can also be applied to adjusting the amount of heat, so it can be used for controlling the brightness and temperature inside a room. Further, as a shutter, it can also be applied to applications for blocking the view from the outside to the inside of a room. Such dimming windows can be applied not only to glass windows for buildings but also to windows of vehicles such as automobiles, trains, airplanes, and ships.

[0131] Moreover, a reflecting member can be provided in one light path of the EC element. Such a window is called an EC mirror and includes a pair of substrates, the EC element according to this embodiment disposed between the pair of substrates, an active element connected to the EC element according to this embodiment, and a reflecting member. The EC mirror may be provided in an automobile or the like as an anti-glare mirror.

[0132] Thus, the EC element 1 containing the organic compound having the skeleton represented by the general formula (1) or the organic compound represented by the general formula (2) in the EC layer 12 can be used for an optical filter, a lens unit, an imaging device, a window material, and the like. Each of the optical filter, the lens unit, the imaging device, and the window material according to the present embodiment can be combined with the organic compound represented by the general formula (1) or the organic compound represented by the general formula (2) alone, or an EC compound having coloring absorption in another wavelength band. Thereby, it becomes possible to provide various absorption colors. Further, since each of the optical filter, the lens unit, the imaging device, and the window material according to the present embodiment contains the organic compound represented by the general formula (1) or the organic compound represented by the general formula (2), the transparency in the bleached state can be improved.

Example

[0133] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto.

[0134] [Example 1] <Synthesis of Exemplary Compound A-5>

[0135]

Chemical formula

[0136] 4-Chloronicotinic acid (2.5 g, 15.7 mmol) and dichloromethane (50 ml) were charged into a reactor and cooled to 0°C. Oxalyl chloride (2.8 ml, 34.5 mmol) and N,N-dimethylformamide (2 ml) were added dropwise to this solution, and then the temperature was raised to room temperature and stirred for 3 hours. The reaction solution was cooled to 0°C, and methanol (5 ml) was added dropwise. After concentrating the reaction solution, ethyl acetate was added to form a suspension. After filtration, washing was performed with ethyl acetate to obtain Intermediate 11 (2.7 g, yield 99%).

[0137]

Chemical formula

[0138] The reactor was charged with intermediate 11 (2.7 g, 15.7 mmol), 1,4-phenylenediboronic acid (1.3 g, 7.1 mmol), 1,4-dioxane (30 mL), and water (10 mL), and the dissolved oxygen was removed with nitrogen. Next, tetrakis(triphenylphosphine)palladium(0) (0.87 g, 0.75 mmol) and tripotassium phosphate (8.4 g, 39.6 mmol) were added under a nitrogen atmosphere, and the reaction was carried out at 100 °C for 8 hours. After cooling the reaction solution, water and ethyl acetate were added, the organic layer was extracted, concentrated, and then recrystallized from toluene / ethyl acetate to obtain intermediate 12 (1.8 g, yield 70%).

[0139]

Chemical formula

[0140] The reaction vessel was charged with intermediate 12 (1.6 g, 4.6 mmol) and anhydrous tetrahydrofuran (60 mL), and cooled to -5 °C. Next, methylmagnesium bromide solution: 36.8 mL (about 1.0 M tetrahydrofuran solution, 36.8 mmol) was slowly added dropwise. After stirring the solution for 1 hour, the temperature was raised to room temperature and stirring was continued for another 6 hours. An aqueous ammonium chloride solution was added to this solution to stop the reaction, then diethyl ether was added, the organic layer was extracted, concentrated, and then recrystallized from toluene / ethanol to obtain intermediate 13 (1.2 g, yield 75%).

[0141]

Chemical formula

[0142] The reaction vessel was charged with intermediate 13 (600 mg, 1.7 mmol) and trifluoromethanesulfonic acid (5 mL), and stirred at room temperature for 5 hours. After neutralizing this solution with an aqueous sodium hydrogen carbonate solution, the precipitated crystals were collected and recrystallized from 2-propanol / hexane to obtain intermediate 14 (484 mg, yield 90%).

[0143] 1The structure of Intermediate 14 was confirmed by 1H NMR measurement.

[0144] 1 1H NMR (CDCl3, 500 MHz) δ (ppm): 8.77 (s, 2H), 8.66 (d, 2H), 7.89 (s, 2H), 7.70 (d, 2H), 1.69 (s, 12H).

[0145] [Chemical formula]

[0146] Intermediate 14 (174 mg, 0.5 mmol), 1-bromoheptane (448 mg, 2.5 mmol), and N,N-dimethylformamide (5 mL) were added to a reaction vessel, and the reaction was carried out at 100 °C for 24 hours. After completion of the reaction, the precipitated solid was filtered and washed with ethyl acetate to obtain 0.30 g (yield: 88%) of Exemplary Compound A-5.

[0147] 1 The structure of Exemplary Compound A-7 was confirmed by 1H NMR measurement.

[0148] 1 1H NMR (DMSO-d6, 500 MHz) δ (ppm): 9.52 (s, 2H), 9.16 (d, 2H), 8.79 (s, 2H), 8.70 (d, 2H), 4.62 (t, 4H), 2.00 (m, 4H), 1.68 (s, 12H), 1.39 - 1.21 (m, 16H), 0.87 (t, 6H).

[0149] [Example 2] [Synthesis of Exemplary Compound A-6] A-5 (201 mg, 0.3 mmol) was dissolved in water. An aqueous solution in which lithium bis(trifluoromethanesulfonyl)imide (0.43 g, 1.5 mmol) was dissolved was added dropwise, and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were filtered and washed successively with isopropyl alcohol and diethyl ether to obtain 283 mg (yield: 88%) of Exemplary Compound A-6.

[0150] 1The structure of Exemplary Compound A-4 was confirmed by 1H NMR measurement.

[0151] 1 1H NMR (CD3CN, 500 MHz) δ (ppm): 8.85 (s, 2H), 8.66 (d, 2H), 8.47 (s, 2H), 8.37 (d, 2H), 4.54 (t, 4H), 2.04 (m, 4H), 1.71 (s, 12H), 1.44 - 1.28 (m, 16H), 0.92 (t, 6H).

[0152] [Example 3] <Synthesis of Exemplary Compound A-40> Intermediate 14 (174 mg, 0.5 mmol), benzyl bromide: 342 mg (2.0 mmol), and acetonitrile (10 mL) were added to a reaction vessel, and the reaction was carried out at 80 °C for 8 hours. After completion of the reaction, the precipitated solid was filtered to obtain 0.30 g of Exemplary Compound A-40 (yield: 92%).

[0153] 1 The structure of Exemplary Compound A-40 was confirmed by 1H NMR measurement.

[0154] 1 1H NMR (D2O, 500 MHz) δ (ppm): 10.04 (s, 2H), 8.79 (d, 2H), 8.38 (s, 2H), 8.34 (d, 2H), 7.45 (s, 10H), 5.75 (s, 4H), 1.59 (s, 12H).

[0155] [Example 4] <Synthesis of Exemplary Compound A-41> Exemplary Compound A-40 (0.13 g, 0.2 mmol) was dissolved in water, and an aqueous solution in which ammonium hexafluorophosphate (200 mg) was dissolved was added dropwise, followed by stirring at room temperature for 3 hours. The precipitated crystals were filtered and washed successively with water, isopropyl alcohol, and diethyl ether to obtain Exemplary Compound A-41 (140 mg, yield: 89%).

[0156] 1 The structure of Exemplary Compound A-41 was confirmed by 1H NMR measurement.

[0157] 1 1H NMR (CD3CN, 500 MHz) δ (ppm): 8.98 (s, 2H), 8.74 (d, 2H), 8.47 (s, 2H), 8.39 (d, 2H), 7.52 (s, 10H), 5.75 (s, 4H), 1.70 (s, 12H).

[0158] [Example 5] [Synthesis of Exemplary Compound A-17] To a reaction vessel were added intermediate 14 (174 mg, 0.5 mmol), ditertiarybutylphenyl iodonium hexafluorophosphate (2.69 g, 5 mmol), copper(II) acetate monohydrate (18 mg, 0.10 mmol), and N,N-dimethylformamide (2.5 mL), and the reaction was carried out at 100 °C for 48 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and an acetonitrile solution (10 ml) of tetrabutylammonium bromide (2 g) was added. The precipitated solid was collected by filtration to obtain Exemplary Compound A-17 (0.24 g, yield: 65%).

[0159] 1 The structure of Exemplary Compound A-17 was confirmed by 1H NMR measurement.

[0160] 1 1H NMR (D2O, 500 MHz) δ (ppm): 9.21 (s, 2H), 8.93 (d, 2H), 8.52 (d, 2H), 8.51 (s, 2H), 7.72 (d, 4H), 7.58 (d, 4H), 5.75 (s, 4H), 1.66 (s, 12H), 1.40 (s, 18H).

[0161] [Example 6] [Synthesis of Exemplary Compound A-18] Exemplary Compound A-17 (0.15 g, 0.2 mmol) was dissolved in water, and an aqueous solution in which 0.3 g of lithium bis(trifluoromethanesulfonyl)imide was dissolved was added dropwise, followed by stirring at room temperature for 3 hours. The precipitated crystals were filtered and washed successively with water, isopropyl alcohol, and diethyl ether to obtain Exemplary Compound A-18 (212 mg, yield: 93%).

[0162] 1The structure of the exemplified compound A-18 was confirmed by 1H NMR measurement.

[0163] 1 1H NMR (CD3CN, 500 MHz) δ (ppm): 9.12 (s, 2H), 8.93 (d, 2H), 8.59 (s, 2H), 8.55 (d, 2H), 7.83 (d, 4H), 7.75 (d, 4H), 5.75 (s, 4H), 1.80 (s, 12H), 1.45 (s, 18H).

[0164] [Example 7] <Fabrication and Characterization of an EC Device> Tetrabutylammonium perchlorate was dissolved in propylene carbonate at a concentration of 0.1 M as an electrolyte, and then the exemplified compound A-6 of Example 2 was dissolved at a concentration of 40.0 mM to obtain an EC solution.

[0165] Next, an insulating layer (SiO2) was formed at the four ends of a pair of glass substrates with transparent conductive films (ITO). A PET film (Melinex S (registered trademark), 125 μm thick, manufactured by Teijin DuPont Films) that defines the substrate interval was placed between the pair of glass substrates with transparent conductive films. Then, leaving an injection port for injecting the EC medium, the substrate and the PET film were adhered and sealed with an epoxy adhesive. As described above, an empty cell with an injection port was fabricated.

[0166] Next, the EC solution obtained above was injected through the aforementioned injection port by a vacuum injection method, and then the injection port was sealed with an epoxy adhesive to obtain an EC device.

[0167] The EC device immediately after fabrication showed a transmittance of around 80% over the entire visible light region and had high transparency.

[0168] When a voltage of 2.5 V was applied to this device, an absorption (λmax = 508 nm) derived from the reduced species of exemplary compound A-6 was exhibited, and the device was colored. Further, when a voltage of -0.5 V was applied, it was decolorized. This device can reversibly change between a colored state and a decolorized state. FIG. 5 is the ultraviolet-visible absorption spectrum of the device fabricated in Example 3. As the light source, a DH-2000S deuterium, halogen light source from Ocean Optics was used.

[0169] [Example 8] In Example 7, a device was fabricated in the same manner as in Example 7, except that exemplary compound A-41 was used instead of exemplary compound A-6. When a voltage of 3.0 V was applied to the device of this example, an absorption (λmax = 511 nm) derived from the reduced species of exemplary compound A-41 was exhibited. Further, when a voltage of -0.5 V was applied, it was decolorized. This device can reversibly change between a colored state and a decolorized state. FIG. 6 is the ultraviolet-visible absorption spectrum of the device fabricated in Example 8.

[0170] [Example 9] In Example 7, a device was fabricated in the same manner as in Example 7, except that exemplary compound A-18 was used instead of exemplary compound A-6. When a voltage of 2.8 V was applied to the device of this example, an absorption (λmax = 536 nm) derived from the reduced species of exemplary compound A-18 was exhibited. Further, when a voltage of -0.5 V was applied, it was decolorized. This device can reversibly change between a colored state and a decolorized state. FIG. 7 is the ultraviolet-visible absorption spectrum of the device fabricated in Example 9.

[0171] [Examples 10 to 12, Comparative Examples 1 and 2] <Evaluation of the reduction potential of the EC device> Tetrabutylammonium perchlorate was dissolved in propylene carbonate at a concentration of 0.1 M as an electrolyte, and then exemplary compound A-13 of Example 2 was dissolved at a concentration of 0.5 mM to obtain an EC solution. Similarly, as Example 11, exemplary compound A-41, as Example 12, exemplary compound A-18, as Comparative Example 1, compound 1-a, and as Comparative Example 2, compound 1-b were dissolved at a concentration of 0.5 mM to obtain an EC solution.

[0172] The measurement was carried out using the BAS electrochemical analyzer model 832B. Carbon was used as the working electrode, platinum as the counter electrode, and Ag / Ag + electrode (propylene carbonate solution of silver hexafluorophosphate) was used, and ferrocene was used as an internal standard for the measurement. The results are shown in Table 1.

[0173]

Table 1

[0174] Among the compounds shown in Table 1, the difference between the first reduction potential and the second reduction potential of Compound 1-a, which is an organic compound described in Patent Document 1, was 0.12 V, and the difference between the first reduction potential and the second reduction potential of Compound 1-b, which is Comparative Example 2, was 0.10 V. In contrast, the differences between the first reduction potential and the second reduction potential of Exemplary Compounds A-6, A-41, and A-18, which are organic compounds according to the present invention, were 0.22 V, 0.22 V, and 0.15 V, respectively. Therefore, the organic compounds according to the present invention are organic compounds having a more stable structure in the first reduction state. Specifically, the organic compounds according to the present invention are organic compounds having a larger difference between the first reduction potential and the second reduction potential.

[0175] From the above, the organic compounds according to the present invention are organic compounds having a more stable structure in the first reduction state. In addition, the organic compounds according to the present invention are organic compounds capable of absorbing light near 500 nm. Further, the organic compounds according to the present invention are more excellent in durability.

[0176] Incidentally, the present invention can also take the following configuration.

[0177] (Configuration 1) An organic compound characterized by being represented by the following general formula (1).

[0178]

Chemical formula

[0179] In general formula (1), X1 and X2 are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group. R1 to R8 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. R 11 to R 14 are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

[0180] (Constitution 2) The organic compound has, as counterions, a monovalent anion A1 - and A2 - The organic compound according to Constitution 1, characterized in that

[0181] (Constitution 3) In general formula (1), X1 and X2 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, The organic compound according to Constitution 1 or 2, characterized in that

[0182] (Constitution 4) In general formula (1), X1 and X2 are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, The organic compound according to any one of Constitutions 1 to 3, characterized in that

[0183] (Constitution 5) In general formula (1), X1 and X2 have the same structure, The organic compound according to any one of Constitutions 1 to 4, characterized in that

[0184] (Constitution 6) In general formula (1), R1 to R8 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and the organic compound according to any one of Configurations 1 to 5.

[0185] (Configuration 7) In general formula (1), R1 to R8 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, a phenyl group, and a methoxy group, and the organic compound according to any one of Configurations 1 to 6.

[0186] (Configuration 8) In general formula (1), R 11 to R 14 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and the organic compound according to any one of Configurations 1 to 7.

[0187] (Configuration 9) In general formula (1), R 11 to R 14 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and the organic compound according to any one of Configurations 1 to 8.

[0188] (Configuration 10) In general formula (1), A1 - and A2 - are each independently selected from Cl - , Br - , I - , BF4 - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - and the organic compound according to Configuration 2.

[0189] (Configuration 11) In general formula (1), A1 - and A2 - are the same anion, and the organic compound according to Configuration 10.

[0190] (Configuration 12) An organic compound that colors upon reduction, Among the plurality of reduction peaks of the organic compound obtained by cyclic voltammetry measurement, when the reduction potential with the largest value is defined as the first reduction potential and the reduction potential with the second largest value after the first reduction potential is defined as the second reduction potential, An organic compound characterized in that the difference between the first reduction potential and the second reduction potential is greater than 0.12 V.

[0191] (Configuration 13) The organic compound according to Configuration 12, characterized in that the organic compound is represented by the following general formula (2).

[0192]

Chemical formula

[0193] In general formula (2), X1 and X2 are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group. R1 to R8 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. R 11 to R 14 are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

[0194] (Configuration 14) An electrochromic element having a pair of electrodes and an electrochromic layer disposed between the pair of electrodes, The electrochromic layer contains an organic compound according to any one of Configurations 1 to 13, and the electrochromic device is characterized by this.

[0195] (Configuration 15) The electrochromic layer has a first organic compound different from the organic compound, and the first organic compound is any one of a phenazine-based compound, a metallocene-based compound, a phenylenediamine-based compound, and a pyrazoline-based compound. The electrochromic device according to Configuration 14 is characterized by this.

[0196] (Configuration 16) The electrochromic layer further has an electrolyte, and the electrochromic device according to Configuration 14 or 15 is characterized by this.

[0197] (Configuration 17) The electrochromic layer further has a thickener, and the electrochromic device according to any one of Configurations 14 to 16 is characterized by this.

[0198] (Configuration 18) An optical filter having the electrochromic device according to any one of Configurations 14 to 17 and an active device connected to the electrochromic device.

[0199] (Configuration 19) A lens unit having the optical filter according to Configuration 18 and an imaging optical system having a lens.

[0200] (Configuration 20) An imaging device having the optical filter according to Configuration 18 and an imaging element that receives light that has passed through the optical filter.

[0201] (Configuration 21) A window, comprising: a pair of substrates; an electrochromic element according to any one of Configurations 14 to 17 disposed between the pair of substrates; and an active element connected to the electrochromic element.

[0202] (Configuration 22) An electrochromic mirror, comprising: an electrochromic element according to any one of Configurations 14 to 17; an active element connected to the electrochromic element; and a reflecting member.

Explanation of Reference Numerals

[0203] 1 EC element 7 Controller 8 Driving power source 9 Resistance switch 10 Transparent substrate 11 Transparent electrode 12 Electrochromic layer 13 Sealing material 20 Driving device 100 Imaging device 101 Optical filter 102 Lens unit 103 Imaging unit 104 First lens group 105 Second lens group 106 Third lens group 107 Fourth lens group 108 Diaphragm 109 Glass block 110 Light receiving element 111 Dimming window 112 Frame 113 Transparent plate

Claims

1. An organic compound represented by the following general formula (1): 【Chemistry 1】 In the general formula (1), X １ and X ２ are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group. １ ~R ８ are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. １１ ~R １４ are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

2. The organic compound is a monovalent anion A １ － and A ２ － 2. The organic compound according to claim 1, which has as a counter ion:

3. In the general formula (1), X １ and X ２ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

4. In the general formula (1), X １ and X ２ and are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms.

5. In the general formula (1), X １ and X ２ The organic compound according to claim 1, characterized in that:

6. In the general formula (1), R １ ~R ８ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having from 1 to 4 carbon atoms, an aryl group having from 6 to 10 carbon atoms, and an alkoxy group having from 1 to 4 carbon atoms.

7. In the general formula (1), R １ ~R ８ are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, a phenyl group, and a methoxy group.

8. In the general formula (1), R １１ ~R １４ The organic compound according to claim 1, characterized in that each of the is independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

9. In the general formula (1), R １１ ~R １４ and are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group.

10. In the general formula (1), A １ － and A ２ － , Cl － , B － , I － , B.F. ４ － , P.F. ６ － , ClO ４ － , C.F. ３ SO ３ － , (CF ３ SO ２ ) ２ N － The organic compound according to claim 2, wherein each of the organic compounds is independently selected from the following:

11. In the general formula (1), A １ － and A ２ － The organic compound according to claim 10, characterized in that:

12. An organic compound which becomes colored when reduced, Among the multiple reduction peaks of the organic compound obtained by cyclic voltammetry measurement, the reduction potential with the largest value is defined as a first reduction potential, and the reduction potential with the second largest value after the first reduction potential is defined as a second reduction potential, An organic compound, wherein the difference between the first reduction potential and the second reduction potential is greater than 0.12 V.

13. The organic compound according to claim 12, characterized in that the organic compound is represented by the following general formula (2): 【Chemistry 2】 In the general formula (2), X １ and X ２ are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group. １ ~R ８ are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. １１ ~R １４ are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

14. An electrochromic element having a pair of electrodes and an electrochromic layer disposed between the pair of electrodes, An electrochromic device, wherein the electrochromic layer contains the organic compound according to claim 1 .

15. The electrochromic element according to claim 14, characterized in that the electrochromic layer has a first organic compound different from the organic compound, and the first organic compound is any one of a phenazine-based compound, a metallocene-based compound, a phenylenediamine-based compound, and a pyrazoline-based compound.

16. 15. The electrochromic device of claim 14, wherein the electrochromic layer further comprises an electrolyte.

17. 15. The electrochromic device of claim 14, wherein the electrochromic layer further comprises a thickener.

18. 15. An optical filter comprising: the electrochromic element according to claim 14; and an active element connected to the electrochromic element.

19. 20. A lens unit comprising: the optical filter according to claim 18; and an imaging optical system having a lens.

20. 20. An imaging device comprising: the optical filter according to claim 18; and an imaging element that receives light that has passed through the optical filter.

21. 21. A window comprising a pair of substrates, an electrochromic element according to any one of claims 14 to 20 disposed between the pair of substrates, and an active element connected to the electrochromic element.

22. 18. An electrochromic mirror comprising: the electrochromic element according to claim 14; an active element connected to the electrochromic element; and a reflecting member.

Images