JP6519101B2 - Electrochromic compound, electrochromic composition, display device and light control device - Google Patents

Description

  The present invention relates to an electrochromic compound that exhibits a black color when colored, an electrochromic composition, and a display device and a light control device using the electrochromic compound or the electrochromic composition.

In recent years, electronic paper has been actively developed as an electronic medium to replace paper.
Electronic paper is characterized in that the display device is used like paper, and therefore, characteristics different from those of conventional display devices such as CRT and liquid crystal display are required. For example, a reflective display device, having high white reflectance and high contrast ratio, capable of high definition display, having a memory effect for display, being capable of driving even at low voltage, being thin and light, being inexpensive And other characteristics are required. Among these, as the characteristics related to the display quality, the demand for white reflectance and contrast ratio equivalent to paper is high.

  So far, as a display device for electronic paper, for example, a method using a reflective liquid crystal, a method using electrophoresis, a method using toner migration, etc. have been proposed, among which the mainstream is the electrophoresis method, At present, it is often used for electronic paper that is on the market as a product. However, in this method, it is particularly difficult to provide high white reflectance, and it has been found that this method shows a very low value of about 40% with 80% of paper and 60% of newsprint. Has become a major issue.

  As a promising technology for solving this problem and realizing a reflective display device, there is a system using an electrochromic phenomenon. By applying a voltage, a phenomenon in which an oxidation-reduction reaction occurs reversibly depending on the polarity and the color changes reversibly is called electrochromism. An electrochromic display device is a display device using color development / decoloration (hereinafter referred to as coloration / decoloration) of an electrochromic compound that causes this electrochromism phenomenon. The electrochromic display device is a reflective display device, has a memory effect, and can be driven at a low voltage, and thus, from material development to device design as a leading candidate for display device technology for electronic paper applications. A wide range of research and development has been conducted. It has been confirmed that the white reflectance in this method is 60%, which is almost equal to that of an actual paper. (Patent Document 1)

  The electrochromic display device is a system that can cover many of the above problems, but the electrochromic compound used in the monochrome display element described in Patent Document 2 made by this system is yellowish. The high white reflectance characteristic of this method could not be realized.

  The present invention has been made in view of the above problems in the prior art, and it is an electrochromic compound that develops a black color, does not have an absorption band at the time of decoloring and has a colorless decoloring state, An electrochromic composition in which a compound is bound or adsorbed to a conductive or semiconductive nanostructure, and a display element having high white reflectance and high contrast, using the electrochromic compound or the electrochromic composition It is an object of the present invention to provide a light control element having high transmittance and high contrast.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by an electrochromic compound having a specific structure, and reached the present invention.
That is, the above-mentioned subject is solved by the electrochromic compound characterized by being denoted by the following general formula (I).

(X1 to X4 in the general formula (1) represent the following general formula (2) or an alkyl group which may have a functional group, an aromatic hydrocarbon group, or a hydrogen atom. At least two or more places. Is represented by the substituent of said General formula (2).)

(In general formula (2), R _{1 to} R ₈ each independently represent a hydrogen atom or a monovalent group, and these monovalent groups may have a substituent. B has a functional group shows good monovalent group optionally, the group of monovalent may have a substituent group .A ^-. the .m representing a monovalent anion is 0-3 general formula (2) And R 1 to R 8, B and m may be each independently different.

  According to the present invention, it is possible to obtain a black-colored electrochromic compound or electrochromic composition which has no absorption band at the time of decoloring and has a colorless decoloring state.

It is the schematic which shows the structural example of the general display element using the electrochromic compound of this invention. It is the schematic which shows the structural example of the general display element using the electrochromic composition of this invention. It is the schematic which shows the structural example of the general light control element using the electrochromic composition of this invention. It is a figure which shows the absorption spectrum in the decoloring state and color development state of the display electrode which formed the electrochromic display layer produced in Example 1. FIG. FIG. 3 is a view showing absorption spectra of the electrochromic display element produced in Example 1 and the electrochromic display element produced in Comparative Example 1 in a decolored state. FIG. 2 is a view showing comparison of color values of the electrochromic display element produced in Example 1 and the electrochromic display element produced in Comparative Example 1. It is a figure which shows the absorption spectrum in the decoloring state and color development state of the display electrode which formed the electrochromic display layer produced in Example 3. FIG. It is a figure which shows the absorption spectrum in the decoloring state and color development state of the display electrode which formed the electrochromic display layer produced in Example 4. FIG. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 5 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 6 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 7 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 8 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 9 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 10 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 11 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 12 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 13 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode which formed the electrochromic display layer produced in Example 14. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 15 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of a display electrode in which the electrochromic display layer produced in Example 16 was formed. It is a figure which shows the absorption spectrum in the decoloring state and color development state of the display electrode which formed the electrochromic display layer produced in Example 17. FIG.

  As described above, as a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved with an electrochromic compound represented by the following general formula (I) . That is, the electrochromic compound represented by the general formula (I) exhibits black coloration and is less colored at the time of decoloring.

(X1 to X4 in the general formula (I) represent the following general formula (II) or an alkyl group which may have a functional group, an aromatic hydrocarbon group or a hydrogen atom. At least two or more places. Is represented by the substituent of said General formula (2).)

(In general formula (2), R _{1 to} R ₈ each independently represent a hydrogen atom or a monovalent group, and these monovalent groups may have a substituent. B has a functional group shows good monovalent group optionally, the group of monovalent may have a substituent group .A ^-. the .m representing a monovalent anion is 0-3 general formula (2) And R 1 to R 8, B and m may be each independently different.

As described above, the present invention relates to the "electrochromic compound" described in the above (1), but this "electrochromic compound" is an "electrochromic compound" described in the following (2) to (9) "Compound" embodiment is included. The present invention also encompasses the “electrochromic composition” and the “display element” described in the following (10) and (11).
Therefore, hereinafter, when the present invention is described in detail, the "electrochromic compound", the "electrochromic composition" and the "display element" described in (2) to (11) are also described in detail.

(2) "The electrochromic compound according to (1), wherein three of X1 to X4 in general formula (I) are represented by general formula (II)". "
(3) The electrochromic compound according to (1), wherein the substitution position in the general formula (II) is any two of X1, X2 and X4 in the general formula (I) ".
(4) “an electrochromic compound characterized by being represented by the following general formula (III);

(In general formula (III), X ₃ represents a hydrogen atom or a monovalent group, and these monovalent groups may have a substituent, and R _{11 to} R ₃₁ each independently represent a hydrogen atom or These monovalent groups may have a substituent, and B ₁ and B ₂ may each independently represent a monovalent group which may have a functional group. valent group may have a substituent .A1 ^-, A2 ^- each represent a monovalent anion)..

(5) “an electrochromic compound represented by the following general formula (IV) or general formula (V);

(In the general formulas (IV) and (V), X ₃ represents a hydrogen atom or a monovalent group, and these monovalent groups may have a substituent. R _{11 to} R ₃₁ are each independently) A hydrogen atom or a monovalent group is shown, and these monovalent groups may have a substituent, and B ₁ and B ₂ may each independently be an aliphatic hydrocarbon group which may have a functional group, Alternatively, an aromatic hydrocarbon group, which may have a substituent .A1 ^-, A2 ^- is .m and n each represents a monovalent anion are independently 1, 2, or 3. Y represents a divalent organic group, and the divalent organic group contains at least one methylene group, and includes an aliphatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group. May)).

(6) "(1) wherein at least one of B, or at least one of B ₁ and B ₂ has a functional group which can be directly or indirectly bonded to a hydroxyl group; The electrochromic compound according to any one of (1) to (5).
(7) “The compound according to the above (6), wherein at least one of X _{1 to} X ₄ of the general formula (I) has a functional group which can be directly or indirectly bonded to a hydroxyl group Electrochromic compound ".
(8) “The functional group capable of being directly or indirectly bonded to the hydroxyl group is a group selected from a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group or a silanol group The electrochromic compound as described in said (6).
(9) "An electrochromic composition comprising the electrochromic compound according to any one of the above (1) to (7) and a conductive or semiconductive nanostructure" bonded or adsorbed.
(10) “The display electrode, the counter electrode provided opposite to the display electrode at a distance from the display electrode, and the electrolyte disposed between the two electrodes, the surface of the display electrode A display layer comprising the electrochromic compound according to any one of (1) to (7) or the electrochromic compound and the electrochromic composition according to (8).
(11) “a display electrode, a counter electrode provided opposite to the display electrode at a distance from the display electrode, and an electrolyte disposed between the two electrodes; The electrochromic compound according to any one of (1) to (7) or the electrochromic compound and the electrochromic composition according to (8), wherein the display electrode, the counter electrode, and the electrolyte are transparent. "Display element".
And by using such an electrochromic compound or electrochromic composition of the present invention, a monochrome display element having high white reflectance and high contrast can be provided. Furthermore, it is possible to provide a monochrome light control device having high transparency and high contrast.

  The electrochromic compound exhibiting black coloration and less coloration at the time of decoloring according to the present invention is represented by the following general formula (I).

(X1 to X4 in the general formula (I) represent the following general formula (II) or an alkyl group which may have a functional group, an aromatic hydrocarbon group or a hydrogen atom. At least two or more places. Is represented by the substituent of said general formula (II).)

(In the general formula (II), R _{1 to} R ₈ each independently represent a hydrogen atom or a monovalent group, and these monovalent groups may have a substituent. B has a functional group shows good monovalent group optionally, the group of monovalent may have a substituent group .A ^-. the .m representing a monovalent anion is 0-3 general formula (2) When it has two or more groups which have the structure of, R < ₁ > -R < ₈ >, B and m may mutually be different, respectively.)

  These electrochromic compounds include, for example, those of the following general formula (VI) to general formula (XII).

(Wherein, R 1 to R 7, B and m have the same meaning as in the case of the general formula (II))

(Wherein, R 1 to R 7, B and m have the same meaning as in the case of the general formula (II), and X 1 has the same meaning as in the case of the general formula (I))

(Wherein, R 1 to R 7, B and m have the same meaning as in the case of the general formula (II), and X 1 and X 2 have the same meaning as in the case of the general formula (I))

(Wherein, R 1 to R 7, B and m have the same meaning as in the case of the general formula (II), and X 1 and X 2 have the same meaning as in the case of the general formula (I))

(Wherein, R 1 to R 7, B and m have the same meaning as in the case of the general formula (II), and X 4 has the same meaning as in the case of the general formula (I))

(Wherein, R 1 to R 7, B and m have the same meaning as in the case of the general formula (II), and X 2 and X 4 have the same meaning as in the case of the general formula (I))

The monovalent groups represented by R1 to R8 in the general formula (II) each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, an amido group, an aminocarbonyl group, Selected from a sulfonic acid group, a sulfonyl group, a sulfonamide group, an aminosulfonyl group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a heterocyclic group And monovalent groups. These monovalent groups may have a substituent. In addition, examples of the monovalent group represented by B include monovalent groups which may each independently have a functional group selected from an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The monovalent group may have a substituent. A ⁻ represents a monovalent anion.
Here, as the above-mentioned carbonyl group which may have a substituent, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group or the like may have a substituent. As a monoalkyl amino carbonyl group, the dialkyl amino carbonyl group, the monoaryl amino carbonyl group, the diaryl amino carbonyl group etc. are mentioned. Examples of the sulfonyl group include an alkoxysulfonyl group, an aryloxysulfonyl group, an alkylsulfonyl group, an arylsulfonyl group and the like. Examples of the aminosulfonyl group which may have a substituent include monoalkylaminosulfonyl group, dialkylaminosulfonyl group, monoarylaminosulfonyl group, and diarylaminosulfonyl group. Examples of the amino group include monoalkylamino group and dialkylamino group. These monovalent groups may have a substituent.
That is, as the monovalent group represented by R1 to R8 in the general formula (II), a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group and an alkoxy optionally having a substituent can be mentioned A carbonyl group, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, an amido group and a substituent Monoalkylaminocarbonyl group which may be substituted, dialkylaminocarbonyl group which may have a substituent, monoarylaminocarbonyl group which may have a substituent, diaryl which may have a substituent An aminocarbonyl group, a sulfonic acid group, an alkoxysulfonyl group which may have a substituent, an aryloxy which may have a substituent A sulfonyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, a sulfonamide group, a monoalkylaminosulfonyl group which may have a substituent, a substituent A dialkylaminosulfonyl group which may have a substituent, a monoarylaminosulfonyl group which may have a substituent, a diarylaminosulfonyl group which may have a substituent, an amino group and a substituent A monoalkylamino group which may be substituted, a dialkylamino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent An alkynyl group which may be substituted, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an arylo which may have a substituent Shi group which may have a substituent alkylthio group which may have a substituent arylthio group, and a heterocyclic group which may have a substituent.
In addition, as the monovalent group represented by B, an alkyl group which may have a functional group, an alkenyl group which may have a functional group, an alkynyl group which may have a functional group, and The aryl group etc. which may have a functional group are mentioned.
These monovalent groups may have a substituent. Further, the above A ⁻ represents a monovalent anion, and is not particularly limited as long as it stably forms a pair with the cation moiety, but Br ion (Br ⁻ ), Cl ion (Cl ⁻ ), ClO _Four ions (ClO ₄ ⁻ ), PF ₆ ions (PF ₆ ⁻ ), BF ₄ ions (BF ₄ ⁻ ) and the like are preferable.
The monovalent group of R1 to R8 can impart the solubility of the electrochromic compound to the solvent, thereby facilitating the device manufacturing process.
The electrochromic compound of the present invention is preferably R1 to R8 and B such that the general formula (I) has a symmetrical structure, from the viewpoint of the easiness of the synthesis and the improvement of the stability.

  The electrochromic compound of the present invention is also one represented by the following general formula (III), (IV) or (V).

(In general formula (III), X ₃ represents a hydrogen atom or a monovalent group, and these monovalent groups may have a substituent. R _{11 to} R ₃₁ each independently represent a hydrogen atom or one These monovalent groups may have a substituent, and B ₁ and B ₂ each independently represent a monovalent group which may have a functional group, and these monovalent groups may be substituted. the groups may have a substituent .A1 ^-, A2 ^- each represent a monovalent anion)..

(5) “an electrochromic compound characterized by being represented by the general formula (IV) or the general formula (V);

(In the general formulas (IV) and (V), X ₃ represents a hydrogen atom or a monovalent group, and these monovalent groups may have a substituent. R _{11 to} R ₃₁ are each independently) A hydrogen atom or a monovalent group is shown, and these monovalent groups may have a substituent, and B ₁ and B ₂ may each independently be an aliphatic hydrocarbon group which may have a functional group, Alternatively, an aromatic hydrocarbon group, which may have a substituent .A1 ^-, A2 ^- is .m and n each represents a monovalent anion are independently 1, 2, or 3. Y represents a divalent organic group, and the divalent organic group contains at least one methylene group, and includes an aliphatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group. May)).

The monovalent group represented by X ₃ in the general formula (III) and the monovalent group represented by R _{11 to} R ₃₁ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, Carboxyl group, carbonyl group, amido group, aminocarbonyl group, sulfonic acid group, sulfonyl group, sulfonamide group, aminosulfonyl group, amino group, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, And monovalent groups selected from an alkylthio group, an arylthio group, and a heterocyclic group. These monovalent groups may have a substituent. In addition, as monovalent groups represented by R ₁ and R ₂ , monovalent groups each of which may have a functional group independently selected from an alkyl group, an alkenyl group, an alkynyl group, and an aryl group are These monovalent groups may have a substituent. A1 ^-, A2 ^- each represent a monovalent anion.
Here, as the above-mentioned carbonyl group which may have a substituent, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group or the like may have a substituent. As a monoalkyl amino carbonyl group, the dialkyl amino carbonyl group, the monoaryl amino carbonyl group, the diaryl amino carbonyl group etc. are mentioned. Examples of the sulfonyl group include an alkoxysulfonyl group, an aryloxysulfonyl group, an alkylsulfonyl group, an arylsulfonyl group and the like. Examples of the aminosulfonyl group which may have a substituent include monoalkylaminosulfonyl group, dialkylaminosulfonyl group, monoarylaminosulfonyl group, and diarylaminosulfonyl group. Examples of the amino group include monoalkylamino group and dialkylamino group. These monovalent groups may have a substituent.
That is, in the general formula (III), as the monovalent group represented by X3 and the monovalent group represented by R11 to R31, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group An alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent An arylcarbonyl group, an amido group, a monoalkylaminocarbonyl group which may have a substituent, a dialkylaminocarbonyl group which may have a substituent, a monoarylaminocarbonyl group which may have a substituent A diarylaminocarbonyl group which may have a substituent, a sulfonic acid group, an alkoxysulfonyl group which may have a substituent, An aryloxysulfonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, a sulfonamide group and a substituent An optionally substituted monoalkylaminosulfonyl group, an optionally substituted dialkylaminosulfonyl group, an optionally substituted monoarylaminosulfonyl group, an optionally substituted diarylaminosulfonyl group Group, amino group, monoalkylamino group which may have a substituent, dialkylamino group which may have a substituent, alkyl group which may have a substituent, and a substituent An alkenyl group which may be substituted, an alkynyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent An aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a heterocyclic group which may have a substituent, etc. Can be mentioned.
In addition, as the monovalent group represented by R ₁ and R ₂ , an alkyl group which may have a functional group each independently, an alkenyl group which may have a functional group, and a functional group are included. And an optionally substituted alkynyl group, an aryl group which may have a functional group, and the like.
These monovalent groups may have a substituent. Furthermore, the ^A1 -, A2 ^- each represents a monovalent anion, but is not particularly limited as long as it forms a cation and stability paired, Br ions ^(Br -), Cl ion ( Cl ⁻ ), ClO ₄ ion (ClO ₄ ⁻ ), PF ₆ ion (PF ₆ ⁻ ), BF ₄ ion (BF ₄ ⁻ ) and the like are preferable.
The solubility of the electrochromic compound in the solvent can be imparted by the monovalent group represented by X3 and the monovalent groups of R11 to R31, which facilitates the device manufacturing process.
The electrochromic compound of the present invention is a monovalent group represented by X3 such that the general formula (III) has a symmetrical structure, and R11 to R31 and B (B ₁ , B ₂ ). Is desirable in terms of the ease of synthesis and the improvement of stability.

Specific examples of monovalent groups represented by X3 in general formula (IV), general formula (V) and monovalent groups represented by R11 to R31 are also exemplified by X3 in general formula (III) And the monovalent group represented by R11 to R31. Further, specific examples of B (B ₁ , B ₂ ) in the general formula (IV) and the general formula (V) are the same as those of B (B ₁ , B ₂ ) in the general formula (III). Further, the anion ^A1 in the general formula (IV), Formula ^{(V) -, A2 -,} A3 -, A4 - also anions ^A1 in the general formula (III) ^-, A2 - is the same as.
Although the specific example of the electrochromic compound of this invention is shown to following structural formula (1)-(72), the electrochromic compound of this invention is not limited to these.
Electrochromic compound (1)

Electrochromic compound (2)

Electrochromic compound (3)

Electrochromic compound (4)

Electrochromic compound (5)

Electrochromic compound (6)

Electrochromic compound (7)

Electrochromic compound (8)

Electrochromic compound (9)

Electrochromic compound (10)

Electrochromic compound (11)

Electrochromic compound (12)

Electrochromic compound (13)

Electrochromic compound (14)

Electrochromic compound (15)

Electrochromic compound (16)

Electrochromic compound (17)

Electrochromic compound (18)

Electrochromic compound (19)

Electrochromic compound (20)

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Electrochromic compound (22)

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Electrochromic compound (25)

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Electrochromic compound (80)

Next, the process for producing the electrochromic compound of the present invention represented by the general formula (1) will be described.
The method for synthesizing the electrochromic compound of the present invention is not particularly limited, and the electrochromic compound can be synthesized by various known coupling methods and the like. For example, when an electrochromic compound of the general formula (III) is synthesized, an enone synthesized by aldol condensation is reacted with an amidine to construct a pyrimidine ring, and then a pyridine ring is formed using an aryl-aryl coupling reaction such as Suzuki coupling. And finally heating in the presence of a halide or the like to quaternize the terminal pyridine.

  In the case of obtaining an electrochromic compound of the general formula (IV), the quaternization reaction is dimerized using about 0.5 times moles of a difunctional compound such as a dihalide, and then again the quaternary ring of the pyridine ring A classification reaction may be performed.

In addition, the electrochromic composition according to the present invention can be obtained by using the electrochromic compound of the present invention [the above-mentioned general formula (I), general formula (III), general formula (IV), or general formula (V) ] Is characterized in that a conductive or semiconductive nanostructure is bound to the compound].
The electrochromic composition of the present invention exhibits black coloration when used in an electrochromic display element, and is further excellent in the image memory property, that is, the color image holding property. The conductive or semiconductive nanostructure is a structure having nanoscale irregularities, such as a nanoparticle or a nanoporous structure.

As described above, in the case where at least one of B ₁ and B ₂ has a functional group that can be directly or indirectly bonded to a hydroxyl group, for example, the electrochromic compound of the present invention serves as a bonding or adsorbing structure When having a sulfonic acid group, a phosphorous acid group (phosphonic acid group), or a phosphoric acid group, or a carboxyl group (carboxylic acid group), the electrochromic compound is easily complexed with the above-mentioned nanostructure, and the color image retention is maintained. The electrochromic composition is excellent. A plurality of the above-mentioned sulfonic acid group, phosphorous acid group or phosphoric acid group, and carboxyl group may be contained in the electrochromic compound. In addition, when the electrochromic compound of the present invention has a silyl group or a silanol group, it is bonded to the above-mentioned nanostructure via a siloxane bond, the bond becomes strong, and a stable electrochromic composition is also obtained. . The siloxane bond referred to here is a chemical bond via a silicon atom and an oxygen atom. In addition, the electrochromic composition may have a structure in which the electrochromic compound and the nano structure are bonded via a siloxane bond, and the bonding method and form thereof are not particularly limited.

  As a material which comprises the said electroconductive or semiconductive nano structure, a metal oxide is preferable from transparency or the surface of electroconductivity. Examples of such metal oxides include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate Metal oxides containing calcium oxide, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate etc. Used. Also, these metal oxides may be used alone, or two or more may be mixed and used.

  In view of electrical properties such as electrical conductivity and physical properties such as optical properties, from metal oxides such as titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, tungsten oxide, etc. When a selected one or a mixture thereof is used, the response speed of coloration and decoloring is excellent. In particular, when titanium oxide is used, the response speed of coloration and decoloring is more excellent.

The shape of the metal oxide is preferably metal oxide fine particles having an average primary particle diameter of 30 nm or less. The smaller the particle size, the better the light transmittance to the metal oxide, and the shape with a large surface area per unit volume (hereinafter referred to as "specific surface area") is used. By having a large specific surface area, the electrochromic compound can be supported more efficiently, and multicolor color display excellent in color display contrast ratio is possible. The specific surface area of the nanostructures is not particularly limited, but can be, for example, 100 m ² / g or more.

Next, the display element according to the present invention will be described.
The display element of the present invention comprises a display electrode, a counter electrode provided opposite to the display electrode at a distance, and an electrolyte disposed between the both electrodes. Having a display layer containing an electrochromic compound represented by the above general formula (I), general formula (III), general formula (IV), or general formula (V) on the surface on the counter electrode side of the display electrode It is characterized by

  The structural example of the general display element which used the electrochromic compound of this invention for FIG. 1 is shown. As shown in FIG. 1, the display element 10 of the present invention comprises a display electrode 1, a counter electrode 2 provided to face the display electrode 1 with a gap, and both electrodes (a counter to the display electrode 1. And an electrolyte 3 in which at least the electrochromic compound (organic electrochromic compound) 4 according to the present invention is dissolved. In this display element, the electrochromic compound is colored and decolored by the redox reaction only on the electrode surface.

FIG. 2 shows an example of the configuration of another general display element using the electrochromic compound of the present invention.
The display element 20 of the present invention is disposed between the display electrode 1, the counter electrode 2 provided opposite to the display electrode 1 with a gap, and both electrodes (the display electrode 1 and the counter electrode 2). And an electrolyte 3. A display layer 5 containing at least the electrochromic composition 4 a of the present invention is provided on the surface of the display electrode 1. In addition, on the display electrode 1 side of the counter electrode 2, a white reflective layer 6 made of white particles is provided.

  As the electrochromic compound in the electrochromic composition of the present invention, a compound having a functional group (adsorbable group) which can be directly or indirectly bonded to a hydroxyl group in the molecular structure, a so-called bonding group is used. be able to. The linking group allows the linking group to bind to the conductive or semiconductive nanostructure to construct an electrochromic composition. The electrochromic composition is provided in layers on the display electrode 1 to form the display layer 5.

Hereinafter, constituent materials used for the electrochromic display elements 10 and 20 according to the embodiment of the present invention will be described.
As a material which comprises the display electrode 1, it is desirable to use a transparent conductive substrate. As a transparent conductive substrate, what coated the transparent conductive thin film on glass or a plastic film is desirable.
The transparent conductive thin film material is not particularly limited as long as it is a material having conductivity, but since it is necessary to ensure light transmittance, a transparent conductive material excellent in transparency and conductivity is used . Thereby, the visibility of the color to be colored can be further enhanced.
As the transparent conductive material, inorganic materials such as tin-doped indium oxide (abbr .: ITO), fluorine-doped tin oxide (abbr .: FTO), and antimony-doped tin oxide (abbr .: ATO) may be used. it can. In particular, it is an inorganic material containing any one of indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide), or zinc oxide (hereinafter referred to as Zn oxide) Is preferred. In oxide, Sn oxide, and Zn oxide are materials which can be easily formed into a film by sputtering, and are materials which can obtain good transparency and electrical conductivity. Particularly preferable materials are InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO.
As a material which comprises the display substrate (code | symbol is non-display) which provides the display electrode 1, glass, a plastics, etc. are mentioned. When a plastic film is used as a display substrate, a lightweight and flexible display element can be manufactured.

As the counter electrode 2, a transparent conductive film such as ITO, FTO or zinc oxide, a conductive metal film such as zinc or platinum, or carbon is used. The opposing electrode 2 is also generally formed on the opposing substrate (not shown). The opposite electrode substrate is also preferably glass or plastic film. When a metal plate such as titanium or zinc is used as the counter electrode 2, the counter electrode 2 also serves as a substrate.
Furthermore, when the material which comprises the counter electrode 2 contains the material which reversely reacts with the oxidation-reduction reaction which the electrochromic composition of a display layer raise | generates, stable coloring and decoloring is possible. That is, when the electrochromic composition develops color due to oxidation, a reduction reaction occurs.
In the case where the electrochromic composition develops a color by reduction, if a material that causes an oxidation reaction is used as the counter electrode 2, the coloration / decoloring reaction in the display layer 5 containing the electrochromic composition becomes more stable.

In general, a material in which a support salt is dissolved in a solvent is used as the material constituting the electrolyte 3.
As the supporting salt, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts and acids, and supporting salts of alkalis can be used. Specific examples include LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , CF ₃ SO ₃ Li, CF ₃ COOLi, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) _{2 and the} like can be used.

Also, as a solvent, for example, propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol , Alcohols are used.
In addition, since it is not particularly limited to a liquid electrolyte in which a support salt is dissolved in a solvent, a gel electrolyte or a solid electrolyte such as a polymer electrolyte may be used. For example, there are solid systems such as perfluorosulfonic acid polymer membranes. Solution systems have the advantage of high ionic conductivity, and solid systems are suitable for producing highly durable devices without degradation.

Moreover, when using the display element of this invention as a reflection type display element, it is desirable to provide the white reflective layer 6 between the display electrode 1 and the counter electrode 2, as shown in FIG. As the white reflective layer 6, it is the simplest method of production to disperse white pigment particles in a resin and apply it on the counter electrode 2.
As the white pigment fine particles, particles composed of general metal oxides can be applied, and specific examples include titanium oxide, aluminum oxide, zinc oxide, silicon oxide, cesium oxide, yttrium oxide and the like. Moreover, it can also serve as a white reflective layer by mixing white pigment particles with a polymer electrolyte.

  As a method of driving the display elements 10 and 20, any method may be used as long as any voltage and current can be applied. An inexpensive display element can be manufactured by using a passive driving method. In addition, high definition and high speed display can be performed by using the active drive method. Active drive can be easily performed by providing an active drive element on the opposite substrate.

FIG. 3 shows an example of the configuration of another general display element using the electrochromic compound of the present invention.
The light control element 30 of this example is disposed between the display electrode 1, the counter electrode 2 provided opposite to the display electrode 1 with a gap, and both electrodes (the display electrode 1 and the counter electrode 2). And the electrolyte 3. And, in the electrolyte 3 on the surface side of the display electrode 1, the display layer 5 including at least the electrochromic composition 4 a of the present invention is provided.
In this display element, the electrochromic compound is colored and decolored by the redox reaction only on the electrode surface. In the light control device, the transparency of the entire device is particularly important.

  As the electrochromic compound in the electrochromic composition of the present invention, a compound having a functional group (adsorbable group) which can be directly or indirectly bonded to a hydroxyl group in the molecular structure, a so-called bonding group is used. be able to. As a result, the binding group can be bound to the conductive or semiconductive nanostructure to constitute an electrochromic composition. The electrochromic composition is provided in layers on the display electrode 1 to form the display layer 5.

Hereinafter, constituent materials used for the electrochromic light control device 30 according to the embodiment of the present invention will be described.
As a material which comprises the display electrode 1, it is necessary to use a transparent conductive substrate. As a transparent conductive substrate, what coated the transparent conductive thin film on glass or a plastic film is desirable.
The transparent conductive thin film material is not particularly limited as long as it is a material having conductivity, but since it is necessary to ensure light transmittance, a transparent conductive material excellent in transparency and conductivity is used . Thereby, the visibility of the color to be colored can be further enhanced.
As the transparent conductive material, inorganic materials such as tin-doped indium oxide (abbr .: ITO), fluorine-doped tin oxide (abbr .: FTO), and antimony-doped tin oxide (abbr .: ATO) may be used. it can. In particular, it is an inorganic material containing any one of indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide), or zinc oxide (hereinafter referred to as Zn oxide) Is preferred. In oxide, Sn oxide, and Zn oxide are materials which can be easily formed into a film by sputtering, and are materials which can obtain good transparency and electrical conductivity. Particularly preferable materials are InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO.
As a material which comprises the display substrate (code | symbol is non-display) which provides the display electrode 1, glass, a plastics, etc. are mentioned. When a plastic film is used as a display substrate, a lightweight and flexible display element can be manufactured.
Like the display electrode 1, the counter electrode 2 also needs to use a transparent conductive substrate. As a transparent conductive substrate, what coated the transparent conductive thin film on glass or a plastic film is desirable.
The transparent conductive thin film material is not particularly limited as long as it is a material having conductivity, but since it is necessary to ensure light transmittance, a transparent conductive material excellent in transparency and conductivity is used . Thereby, the visibility of the color to be colored can be further enhanced.

As the transparent conductive material, inorganic materials such as tin-doped indium oxide (abbr .: ITO), fluorine-doped tin oxide (abbr .: FTO), and antimony-doped tin oxide (abbr .: ATO) may be used. it can. In particular, it is an inorganic material containing any one of indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide), or zinc oxide (hereinafter referred to as Zn oxide) Is preferred. In oxide, Sn oxide, and Zn oxide are materials which can be easily formed into a film by sputtering, and are materials which can obtain good transparency and electrical conductivity. Particularly preferable materials are InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO.
As in the case of the display electrode 1, glass, plastic or the like may be mentioned as a material for forming the display substrate (the reference numeral is not displayed) on which the counter electrode 2 is provided. When a plastic film is used as a display substrate, a lightweight and flexible display element can be manufactured.
Furthermore, when the material which comprises the counter electrode 2 contains the material which reversely reacts with the oxidation-reduction reaction which the electrochromic composition of a display layer raise | generates, stable coloring and decoloring is possible. That is, when the electrochromic composition causes a reduction reaction when it develops color due to oxidation, and when the electrochromic composition causes an oxidation reaction when it develops color due to reduction, a display layer containing the electrochromic composition is used. The color reaction of 5 is more stable.
In general, a material in which a support salt is dissolved in a solvent is used as the material constituting the electrolyte 3. In the case of the light control element, in particular, the electrolyte 3 needs to be colorless and transparent.
As the supporting salt, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts and acids, and supporting salts of alkalis can be used. Specific examples include LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , CF ₃ SO ₃ Li, CF ₃ COOLi, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) _{2 and the} like can be used.
Moreover, as a solvent, for example, propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol , Alcohols are used.
In addition, since it is not particularly limited to a liquid electrolyte in which a support salt is dissolved in a solvent, a gel electrolyte or a solid electrolyte such as a polymer electrolyte may be used. For example, there are solid systems such as perfluorosulfonic acid polymer membranes. Solution systems have the advantage of high ionic conductivity, and solid systems are suitable for producing highly durable devices without degradation.
As a method of driving the light adjustment device 30, any method may be used as long as an arbitrary voltage and current can be applied. By using the passive drive method, it is possible to manufacture an inexpensive light adjustment device. In addition, high-definition and high-speed dimming can be performed by using a transparent active drive element. For example, IGZO etc. are mentioned as a transparent active drive element.

  EXAMPLES Hereinafter, the electrochromic compound and the electrochromic composition of the present invention, and a display element or a light control element using them according to examples will be described, but the present invention is not limited to these examples.

Example 1
<Synthesis of Electrochromic Compound [Structural Formula (19)]>
<a> Synthesis of Intermediate (19-1)

In a 100 mL three-necked eggplant flask, 9.25 g (50 mmol) of 4-bromobenzaldehyde and 9.94 g (50 mmol) of 4-bromoacetophenone were added and dissolved in 50 ml of methanol. Further, under nitrogen atmosphere, 0.10 g (2.25 mmol) of sodium hydroxide was added and stirred at room temperature for 6 hours. After completion of the reaction, the substance obtained by filtration was washed with distilled water and methanol to obtain the desired product as a yellow powder.
This intermediate (19-1) was Mp; 184.5-185.5 ° C (lit. 183-184 ° C).
Yield 17.0 g, 92.9%.

<B> Synthesis of Intermediate (19-2)

Intermediate (19-1) 10.0 g (27.3 mmol) and (94%) (benzamidine hydrochloride) 2.28 g (13.7 mmol) were dissolved in 70 ml of ethanol. To this, 50 ml of ethanol in which 1.80 g (32.1 mmol) of potassium hydroxide (85%) was dissolved was added dropwise over 15 minutes and then refluxed for 24 hours. This was washed with distilled water and the product was purified by silica gel chromatography (toluene). The crude product was further recrystallized in toluene / hexane for purification to obtain the desired product.
This intermediate (19-2) was Mp; 204.5-205.0 ° C (lit. 203-205 ° C).
Yield 5.06 g, yield 39.8%.

<C> Synthesis of Intermediate (18-3)

In a 100 mL three-necked eggplant flask, 10 mL of previously degassed toluene and 2 mL of ethanol are added, and 0.47 g (1.0 mmol) of intermediate (22-2) and 0.62 g (3.0 mmol) of 4-pyridineboronic acid pinacol ester Dissolved. 36 mg (0.03 mmol; 3 mol%) of tetrakis (triphenylphosphine) palladium and 2.5 g of a 2 M aqueous solution of potassium carbonate were added while flowing nitrogen into an eggplant flask and refluxed for 14 hours. Then, toluene was added to the solution to extract the organic layer, and the solution was further washed with distilled water.
After adding magnesium sulfate as a desiccant to this organic layer and dehydrating it, the solvent was distilled off under reduced pressure. The obtained crude product is then refluxed with a mixed solvent of ethanol / ethyl acetate to obtain the desired product as a colorless powder.
Yield 0.34 g, yield 72.3%.

<D> Synthesis of electrochromic compound (19) [Structural formula (19)]

In a 25 ml three-necked flask, 0.113 g (0.40 mmol) of intermediate (19-3), 0.358 g (1.35 mmol) of 4-bromomethylbenzylphosphonic acid, 3.0 ml of dimethylformamide are added, and the mixture is heated at 90.degree. It was allowed to react for 2 hours. After returning to room temperature, this solution is discharged into 2-propanol, and then the obtained solid is dispersed in 2-propanol, then recovered, and dried under reduced pressure at 100 ° C. for 2 days to obtain the desired product. The
Yield 0.29 g, 90% yield.

[Preparation and Evaluation of Electrochromic Display Element]
(A) Formation of Display Electrode and Electrochromic Display Layer First, a 25 mm × 30 mm glass substrate with an FTO conductive film (manufactured by AGC Fabritech Co., Ltd.) is prepared, and titanium oxide nanoparticle dispersion is prepared in the 19 mm × 15 mm region on the top surface thereof. A titanium oxide particle film was formed by coating (SP210 manufactured by Showa Titanium Co., Ltd.) by spin coating and annealing at 120 ° C. for 15 minutes.
The titanium oxide particle film is coated with a 1 wt% 2,2,3,3-tetrafluoropropanol solution of a compound represented by the structural formula (19) as a coating solution by spin coating, and annealing is performed at 120 ° C. for 10 minutes Thus, the display layer 5 was formed by adsorbing the electrochromic compound on the surface of the titanium oxide particles.
The configuration of the electrochromic display element produced is in accordance with the configuration of FIG. 2 (except for the white reflective layer).

(B) Formation of White Reflective Layer Furthermore, a solution in which 10 wt% of urethane paste (HW140SF manufactured by DIC Corporation) is dissolved as a binding polymer in 2,2,3,3-tetrafluoropropanol solution is prepared. A paste in which 50 wt% of titanium oxide particles (trade name: CR90, manufactured by Ishihara Sangyo Co., Ltd., average particle diameter: about 250 nm) is dispersed is applied to the surface of the electrochromic layer by spin coating and annealed at 120 ° C for 5 minutes Thus, a white reflective layer of about 1 μm was formed.

(C) Formation of Counter Electrode On the other hand, a 25 mm × 30 mm glass substrate with an ITO conductive film (manufactured by Geomatec Co., Ltd.) was prepared separately from the glass substrate and used as a counter substrate.

(D) Preparation of Electrochromic Display Element A display substrate and an opposite substrate were bonded through a 75 μm spacer to fabricate a cell. Next, an electrolyte solution was prepared by dissolving 20 wt% of tetrabutylammonium perchlorate in dimethylsulfoxide, and the solution was enclosed in a cell to fabricate an electrochromic display element.

Comparative Example 1
The electrochromic compound represented by following Structural formula (82) shown by [Chemical formula 46] described in patent document 2 (Unexamined-Japanese-Patent No. 2011-102287) was synthesize | combined.

  A display electrode and an electrochromic display layer were formed in the same manner as in (a) to (d) of Example 1 except that the obtained electrochromic compound was used, to produce an electrochromic display element.

[Coloring and decoloring comparison test 1]
The display electrodes (a) on which the electrochromic display layers produced in Example 1 and Comparative Example 1 were formed were respectively put in a quartz cell, and a platinum electrode as a counter electrode and an Ag / Ag + electrode as a reference electrode (BAS RE Co., Ltd. RE Using -7), the inside of the cell was filled with an electrolytic solution in which 0.1 M of tetrabutylammonium perchlorate was dissolved in dimethyl sulfoxide. The quartz cell was irradiated with deuterium tungsten halogen light (Ocean Optics DH-2000), and the transmitted light was detected by a spectrometer (Ocean Optics USB4000) to measure an absorption spectrum. The absorption spectra in the bleached state and in the colored state are shown in FIG.
In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

  The comparison of the absorption spectrum in the decoloring state of the electrochromic display layer (d) of Example 1 and the electrochromic display layer (d) of Comparative Example 1 is shown in FIG. In Comparative Example 1, absorption was observed at around 400 nm even in the decolored state, and the decolored material was more colored than the electrochromic compound of Example 1.

With respect to each of the electrochromic display elements (d) manufactured in Example 1 and Comparative Example 1, comparative evaluation of coloration and decolorization was carried out. The evaluation of the coloration / discoloring was performed by irradiating the diffused light using a spectrocolorimeter MCPD 7700 manufactured by Otsuka Electronics Co., Ltd. Color values were evaluated in the CIE L * a * b * color space, and a * vs b * were plotted in FIG.
In the colored state after application of a voltage of -6.0 V to each display element, both of the electrochromic display elements of Example 1 and Comparative Example 1 are very close to the origin of the a * vs b * plot and substantially similar to black. I was able to confirm that I was coloring.

In the decolored state before voltage application, Example 1 shows almost the same color tone in the a * vs b * plot as compared with Japan Color White plotted at the origin.
On the other hand, regarding Comparative Example 1, the value of b * was large, and it was found that there was yellowish color.
From the above results, when the electrochromic display elements of Example 1 and Comparative Example 1 are compared, it can be seen that Example 1 is less colored in the decolored state and higher in white reflectance.

Example 2
[Preparation and evaluation of electrochromic light control device]
(A) Formation of Display Electrode and Electrochromic Display Layer First, a 25 mm × 30 mm glass substrate with an FTO conductive film (manufactured by AGC Fabritech Co., Ltd.) is prepared, and titanium oxide nanoparticle dispersion is prepared in the 19 mm × 15 mm region on the top surface thereof. A titanium oxide particle film was formed by coating (SP210 manufactured by Showa Titanium Co., Ltd.) by spin coating and annealing at 120 ° C. for 15 minutes.
The titanium oxide particle film is applied by spin coating using a 1 wt% 2,2,3,3-tetrafluoropropanol solution of compound (19) represented by the structural formula (19) as a coating solution, and annealed at 120 ° C. for 10 minutes By performing the treatment, a display layer 5 in which the electrochromic compound is adsorbed on the surface of the titanium oxide particles was formed.
In addition, the structure of the electrochromic light control element of preparation conforms to the structure of FIG. 3 (except for a white reflective layer).

(B) Formation of Counter Electrode On the other hand, a 25 mm × 30 mm glass substrate with an ITO conductive film (manufactured by Geomatec) was prepared separately from the glass substrate, and used as a counter substrate.

(C) Production of Electrochromic Light Adjusting Device A display substrate and an opposite substrate were bonded to each other through a 75 μm spacer to produce a cell. Next, an electrolyte solution was prepared by dissolving 20 wt% of tetrabutylammonium perchlorate in dimethyl sulfoxide, and the solution was enclosed in a cell to fabricate an electrochromic light control device.

[Coloring and decoloring comparison test 2]
The light control element (c) manufactured in Example 2 is irradiated with deuterium tungsten halogen light (Ocean Optics DH-2000), the transmitted light is detected by a spectrometer (Ocean Optics USB 4000), and the transmission spectrum is measured. did. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. In particular, the transmittance at 550 nm showed 80%. On the other hand, when voltage was applied to this element at -6.0 V for 2 seconds, it was confirmed that black color was developed and the transmittance at 550 nm was reduced to 10%.

[Example 3]
<Synthesis of Electrochromic Compound (26) [Structural Formula (37)]>
<a> Synthesis of Intermediate (37-1)

Intermediate (37-1)

  The target compound was obtained by using acetamidine hydrochloride in place of benzamidine hydrochloride by the same synthesis route as in Example 1 <b> using the intermediate (18-1) synthesized in <a> in Example 1. .

<C> Synthesis of Intermediate (37-2)

Intermediate (37-2)

  Intermediate (37-1) and 4-pyridineboronic acid pinacol ester were reacted according to the same synthetic route as in Example 1 <c> to obtain the desired product.

<D> Synthesis of electrochromic compound (37) [structural formula (37)]

Compound (37)

  The intermediate (37-2) and 4-bromomethylbenzyl phosphonic acid were used in the same manner as in Example 1 <c> to give the desired product as a colorless powder.

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and Evaluation of Electrochromic Display Element] was performed to prepare an electrochromic display element using the compound (37) of Structural Formula (37) as a coloring dye.

[Coloring and decoloring test 3]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

Example 4
<Synthesis of Electrochromic Compound (27) [Structural Formula (27)]>
<a> Synthesis of Intermediate (27-1)

Intermediate (27-1)

  Example 1 <a> In the synthesis method of intermediate (26-1), 4-acetyl-4'-bromobiphenyl was used instead of 4-bromoacetophenone to make a reaction to obtain the desired product.

<B> Synthesis of Intermediate (27-2)

Intermediate (27-2)

  Example 1 <b> The desired compound was obtained from the intermediate (27-1) by the same synthesis method.

<C> Synthesis of Intermediate (27-3)

Intermediate (27-3)

  The target compound was obtained from the intermediate (27-2) by the same synthesis method as in Example 1 <c>.

<D> Synthesis of electrochromic compound (27) [structural formula (27)]

Compound (27)

  The intermediate (27-3) was used in the same manner as in Example 1 <c> to give the desired product.

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element having a structural formula (27) as a coloring dye.

[Coloring and decoloring test 4]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. The absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 5]
<Synthesis of Electrochromic Compound (51) [Structural Formula (51)]>
<a> Synthesis of Intermediate (51-1)

The flask was charged with 4,6-dichloropyrimidine (596 mg, 4 mmol), replaced with argon gas, then degassed with argon gas (60 mL), 4- (4,4,5,5-tetramethyl- 1,3,2-Dioxaborolan-2-yl) pyridine (8 mmol, 1.64 g), bis (triphenylphosphine) palladium (II) dichloride (0.2 mmol, 140 mg) were added ¹ . After bubbling the solution with argon gas, 2 M aqueous potassium carbonate solution (20 mL) was added, and heating and stirring were performed at 100 ° C. for 8 hours. The contents were filtered through Celite, water and chloroform were added to the filtrate to separate the organic layer, and the aqueous layer was extracted five times with chloroform. The combined organic layer was washed with saturated brine and then dried over sodium sulfate, and the filtrate was concentrated to give a crude product. This is purified by silica gel chromatography (developing solvent chloroform / methanol = 93/7), the obtained solid is washed with chloroform / hexane, the solid collected by filtration is vacuum dried, and the intermediate (51) is obtained as a pale yellow solid. -1) obtained (yield 268 mg, 29%)
¹ H NMR (500 MHz, CDCl ₃ , δ): 9.46 (d, J = 1.7 Hz, 1 H), 8.86 (dd, J ₁ = 4.0 Hz, J ₂ = 1.7 Hz, 4 H), 8.21 (d, J = 1.7 Hz, 1 H), 8.04 (dd, J ₁ = 4.6 Hz, J ₂ = 1.7 Hz, 4 H)

(B) Synthesis of electrochromic compound (51) [structural formula (51)]

  The intermediate (51-1) (234 mg, 1 mmol), bromooctyl phosphonic acid (1.09 g, 4 mmol), DMF (10 mL) was placed in a flask, and heat expansion at 100 ° C. for 4 hours was stated. After adding DMF under reduced pressure, 2-propanol was added to the residue, and the precipitated solid was filtered and vacuum dried to obtain the desired product as a yellow solid. Yield 702 mg, 90% yield.

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and Evaluation of Electrochromic Display Element] was performed to prepare an electrochromic display element using the compound (51) of Structural Formula (51) as a coloring dye.

[Coloring and decoloring test 5]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. The absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 6]
<Synthesis of Electrochromic Compound (50) [Structural Formula (50)]>
<a> Synthesis of Intermediate (50-1)

In Example 5, 4- (4-pyridyl) phenylboronic acid pinacol ester in place of 4- (4,4,5,5-tetramethyl-1,3,2-hourly saborolan-2-yl) pyridine The reaction and purification were carried out in the same manner as except using, to obtain an intermediate (48-1). (Yield 592 mg, 38% yield)
1 H NMR (500 MHz, CDCl ₃ , δ): 9.39 (d, J = 1.8 Hz, 1 H), 8.73 (dd, J ₁ = 4.6 Hz, J ₂ = 2.2 Hz, 4 H), 8.32 (d, J = 8.6 Hz, 4 H), 8.22 (d, J = 1.2 Hz, 1 H), 7. 85 (d, J = 8.6 Hz, 4 H), 7. 60 (dd, J ₁ = 4.6 Hz, J ₂ = 1.2 Hz, 4 H)

<B> Synthesis of electrochromic compound (50) [Structural formula (50)]

  The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 830 mg, 89% yield)

[Preparation and Evaluation of Electrochromic Display Element] In Example 1, the same procedure as described in [Preparation and Evaluation of Electrochromic Display Element] is carried out to color a compound (50) of the structural formula (50) An electrochromic display element was prepared as a dye.

[Coloring and decoloring test 6]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. The absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 7]
<Synthesis of Electrochromic Compound (78) [Structural Formula (78)]>
<a> Synthesis of Intermediate (78-1)

A reaction and purification were performed in the same manner as in Example 6 except that 4,6-dichloropyrimidine in Example 6 was changed to 2, 4-dichloropyrimidine, to obtain an intermediate (78-1). Yield 1.39 g, 90% yield.
¹ H NMR (500 MHz, CDCl ₃ , δ): 8.92 (d, J = 5.7 Hz, 1 H), 8.71-8.74 (m, 6 H), 8.38 (dd, J ₁ = 6.3 Hz, J ₂ = 1.7 Hz 2 H ), 7.82-7.85 (m, 4H), 7.70 (d, J = 5.3 Hz, 1H), 7.59-7.62 (m, 4H)

<B> Synthesis of electrochromic compound (78) [structural formula (78)]

  The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 793 mg, 85% yield).

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (78) of the structural formula (78) as a coloring dye.

[Coloring and decoloring test 7]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. The absorption spectra in the decolored state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 8]
<Synthesis of Electrochromic Compound (79) [Structural Formula (79)]>
<a> Synthesis of Intermediate (79-1)

A reaction and purification were performed in the same manner as in Example 6 except that 4,6-dichloropyrimidine in Example 6 was changed to 2,4,6-trichloropyrimidine, to obtain an intermediate (79-1). Yield 1.56 g, 72% yield.
¹ H NMR (500 MHz, CDCl ₃ , δ): 8.87 (d, J = 8.6 Hz, 2 H), 8.75-8.72 (m, 6 H), 8.15 (s, 1 H), 8.46 (d, J = 8.6 Hz, 4H), 7.89-7.85 (m, 6H), 7.64-7.61 (m, 6H)

<B> Synthesis of electrochromic compound (79) [structural formula (79)]

  The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 1.09 g, 80% yield).

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (78) of the structural formula (79) as a coloring dye.

[Coloring and decoloring test 8]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 9]
<Synthesis of Electrochromic Compound (44) (Structural Formula (44))>
<a> Synthesis of Intermediate (44-1)

The flask is charged with 4,6-dichloropyrimidine (596 mg, 4.0 mmol), and after substitution with argon gas, dioxane (60 mL) degassed with argon gas, 4- (4-pyridyl) phenylboronic acid pinacol ester (4.0 mmol, 2.26 g), bis (triphenylphosphine) palladium (II) dichloride (0.3 mmol, 210 mg) was added. The solution was bubbled with argon gas, 2 M K ₂ CO ₃ (20 mL) was added, and the mixture was heated and stirred at 50 ° C. for 4 hours. Next, 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (4 mmol, 820 mg) was added, and heating and stirring were performed at 100 ° C. for 4 hours. Subsequently, the contents were filtered through Celite, water and chloroform were added to the filtrate to separate the organic layer, and the aqueous layer was extracted 5 times with chloroform. The combined organic layer was washed with saturated brine and then dried over sodium sulfate, and the filtrate was concentrated to give a crude product. This is purified by silica gel chromatography (developing solvent chloroform / methanol = 93/7), the obtained solid is washed with chloroform / hexane, the solid collected by filtration is dried under vacuum, and the intermediate (44 as a pale yellow solid) -1) (yield 892 mg, 72%).
¹ H NMR (500 MHz, CDCl ₃ , δ): 9.42 (d, J = 1.7 Hz, 1 H), 8. 85 (dd, J ₁ = 5.8 Hz, J ₂ = 1.8 Hz, 2 H), 8.73 (dd, J _{1 = 6.3 Hz, J 2 = 1.7} Hz, 2H), 8.31 (d, J = 8.6 Hz, 2H), 8.21 (d, J = 1.7 Hz, 1H), 8.04 (dd, J 1 = 6.3 Hz, J 2 = 1.7 Hz, 2 H), 7.84 (d, J = 6.9 Hz, 2 H), 7. 59 (d, J ₁ = 5.8 Hz, J ₂ = 1.8 Hz, 2 H)

<B> Synthesis of electrochromic compound (44) [structural formula (44)]

The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 771 mg, 90% yield).
[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (44) of the structural formula (44) as a coloring dye.

[Coloring and decoloring test 9]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 10]
<Synthesis of Electrochromic Compound [Structural Formula (80)]>
<a> Synthesis of Intermediate (53-1)

The flask was charged with 2,4,6-trichloropyrimidine (732 mg, 4.0 mmol), replaced with argon gas, and then degassed with argon gas (60 mL), 4- (4-pyridyl) phenyl Boronic acid pinacol ester (8.0 mmol, 2.26 g), bis (triphenylphosphine) palladium (II) dichloride (0.3 mmol, 210 mg) were added. After bubbling the solution with argon gas, 2 M K ₂ CO ₃ (20 mL) was added, and heating and stirring were performed at 50 ° C. for 4 hours. Next, 4-4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (4 mmol, 820 mg) was added, and heating and stirring were performed at 100 ° C. for 4 hours. Subsequently, the contents were filtered through Celite, water and chloroform were added to the filtrate to separate the organic layer, and the aqueous layer was extracted 5 times with chloroform. The combined organic layer was washed with saturated brine and then dried over sodium sulfate, and the filtrate was concentrated to give a crude product. This is purified by silica gel chromatography (developing solvent chloroform / methanol = 93/7), the obtained solid is washed with chloroform / hexane, the solid collected by filtration is dried under vacuum, and the intermediate (80 as a pale yellow solid) -1) (yield 1.19 g, yield 64%).
¹ H NMR (500 MHz, CDCl ₃ , δ): 8.87 (dd, J ₁ = 4.7 Hz, J ₂ = 1.7 Hz, 2 H), 8. 75 (dd, J ₁ = 4.0 Hz, J ₂ = 1.7 Hz, 4 H) , 8.58 (dd, J ₁ = 4.7 Hz, J ₂ = 1.7 Hz, 2 H), 8. 45 (dt J ₁ = 8.0 Hz, J ₂ = 1.7 Hz, 4 H), 8.21 (s, 1 H), 7. 88 (dd, J ₁ = 8.6 Hz, J ₂ = 1.7 Hz, 4 H), 7.61 (dd, J ₁ = 4.7 Hz, J ₂ = 1.7 Hz, 4 H)

<B> Synthesis of electrochromic compound [Structural formula (80)]

  The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 1.06 g, 83% yield).

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (80) of the structural formula (80) as a coloring dye.

[Coloring and decoloring test 10]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. The absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 11]
<Synthesis of Electrochromic Compound (36) [Structural Formula (36)]>
<a> Synthesis of Intermediate (36-1)

  In place of the intermediate (44-1) used in Example 9, the intermediate (50-1) already obtained in Example 6 is used. The same reaction and purification were carried out except that 5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine was changed to 4- (trifluoromethyl) phenylboronic acid, to give intermediate (36-1) Obtained. Yield 740 mg 65%.

<B> Synthesis of electrochromic compound (36) [structural formula (36)]

  The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 915 g, 85% yield).

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (36) of the structural formula (36) as a coloring dye.

[Coloring and decoloring test 11]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. The absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 12]
<Synthesis of Electrochromic Compound (38) [Structural Formula (38)]>
<a> Synthesis of Intermediate (38-1)

  In place of the intermediate (44-1) used in Example 9, the intermediate (50-1) already obtained in Example 6 is used. A reaction and purification were carried out in the same manner except that 5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine was changed to 4- (cyano) phenylboronic acid, to give an intermediate (38-1) . Yield 304 mg, yield 16%.

<B> Synthesis of electrochromic compound (38) [structural formula (38)]

  The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 919 mg, 89% yield)

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (38) of the structural formula (38) as a coloring dye.

[Coloring and fading test 12]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 13]
<Synthesis of Electrochromic Compound (42) [Structural Formula (42)]>
<a> Synthesis of Intermediate (42-1)

  In place of the intermediate (44-1) used in Example 9, the intermediate (50-1) already obtained in Example 6 is used. The same reaction and purification were carried out except that 5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine was changed to 4- (2,6-difluoro) phenylboronic acid, to give an intermediate (42-1 Got). Yield 396 mg, 21% yield.

<B> Synthesis of electrochromic compound (42) [structural formula (42)]

The reaction and purification were carried out in the same manner as in Example 5 to obtain the desired product. (Yield 835 mg, 80% yield)
[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (42) of the structural formula (42) as a coloring dye.

[Coloring and fading test 13]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. The absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

Example 14
<Synthesis of Electrochromic Compound (31) [Structural Formula (31)]>
<a> Synthesis of Intermediate (31-1)

  In place of the intermediate (44-1) used in Example 9, the intermediate (50-1) already obtained in Example 6 is used. A reaction and purification were carried out in the same manner except that 5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine was changed to a compound of the following structural formula to obtain an intermediate (31-1). Yield 1.74 g, 73% yield.

<B> Synthesis of Intermediate (31-2)

  The flask was charged with the intermediate (31-1) (0.338 mmol, 207 mg) synthesized above, n-butyl bromide (1.35 mmol, 184 mg), and DMF (15 mL), and stirred at 85 ° C. for 12 hours. The DMF was distilled off under reduced pressure, acetone was added to the residue, and the precipitated solid was collected by filtration and dried under reduced pressure to obtain an intermediate (31-2). Yield 278 mg, 92% yield.

<C> Synthesis of electrochromic compound (31) [Structural formula (31)]

The intermediate (31-2) (277 mg, 0.312 mmol) and chloroform (50 mL) were put into a flask, trimethylsilyl bromide (50 mL) was added dropwise, and the mixture was stirred at room temperature for 16 hours. Chloroform was distilled off under reduced pressure, methanol was added to the residue, and the mixture was stirred for 1 hour. Methanol was distilled off under reduced pressure, acetone was added to the residue, and the precipitated solid was collected by filtration to obtain the desired product. Yield 204 mg, yield 78%.
¹ H NMR (500 MHz, CDCl ₃ , δ): 9.20 (d, J = 6.9 Hz, 4 H), 8. 85 (s, 1 H), 8. 80 (d, J = 8.6 Hz, 4 H), 8. 69 (d, J = 6.9 Hz, 4 H), 8.61 (d, J = 8.0 Hz, 2 H), 8. 36 (d, J = 8.6 Hz, 4 H), 7.51 (dd, J1 = 6.3 Hz, J2 = 2.3 Hz, 2 H), 4.64 (t , J = 6.9 Hz, 4 H), 3. 12 (d, J = 21.8 Hz, 2 H), 1. 96 (quint, J = 7.5 Hz, 4 H), 1. 37 (quin t, J = 7.5 Hz, 4 H), 0.96 (t, J = 7.5 Hz, 6 H)

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and Evaluation of Electrochromic Display Element] was performed to prepare an electrochromic display element using the compound (31) of Structural Formula (31) as a coloring dye.

[Coloring and decoloring test 14]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 15]
<Synthesis of Electrochromic Compound [Structural Formula (35)]>
<a> Synthesis of Intermediate (35-1)

The reaction and purification were carried out in the same manner as in Example 14 except that n-butyl bromide in step 14 (b) above was changed to 2,2,2-trifluoroethyl trifluoromethanesulfonate, and an intermediate (35-) was obtained. I got 1).
Yield 132 mg, 60% yield.

<C> Synthesis of electrochromic compound (35) [structural formula (35)]

Instead of Intermediate (31-2) of Example 14 (c) step except for using an intermediate (35-1) performs reaction and purification in the same manner as in Example 14, the desired product (OTf ^- is To give a triflate anion). Yield 119 mg, 95% yield.
¹ H NMR (500 MHz, CDCl ₃ , δ): 9.30 (d, J = 6.3 Hz, 4 H), 8.83-8.88 (m, 9 H), 8.62 (d, J = 8.0 Hz, 2 H), 8.40 (d, J = 8.6 Hz, 4 H), 7.52 (dd, J ₁ = 8.0 Hz, J ₂ = 1.7 Hz, 2 H), 5. 86 (q, J = 8.6 Hz, 4 H), _{3. 13} (d, J = 21.2 Hz, 2 H)

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (35) of the structural formula (35) as a coloring dye.

[Coloring and decoloring test 15]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 16]
<Synthesis of Electrochromic Compound [Structural Formula (56)]>
<a> Synthesis of Intermediate (56-1)

  In place of the intermediate (44-1) used in Example 9, the intermediate (50-1) already obtained in Example 6 is used. A reaction and purification were carried out in the same manner except that 5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine was changed to a compound of the following structural formula to obtain an intermediate (56-1). Yield 1.86 g, 74% yield.

<a> Synthesis of Intermediate (56-2)

  Example 14 (b) A reaction and purification were carried out in the same manner except that intermediate (31-1) was changed to intermediate (56-1) in the step, and intermediate (56-2) was obtained. Yield 304 mg, 90% yield.

<C> Synthesis of electrochromic compound (56) [structural formula (56)]

A reaction and purification were performed in the same manner as in Example 14 except that the intermediate (31-2) in the step of Example 14 (c) was changed to the intermediate (56-2), to obtain a desired product. Yield 244 mg, 95% yield.
¹ H NMR (500 MHz, CDCl ₃ , δ): 9.21 (d, J = 7.5 Hz, 4 H), 8. 85 (s, 1 H), 8. 80 (d, J = 8.6 Hz, 4 H), 8. 69 (d, J = 6.9 Hz, 4 H), 8.62 (d, J = 8.0 Hz, 2 H), 8. 36 (d, J = 8.6 Hz, 4 H), 7.51 (d, J = 8.0 Hz, 2 H),. 4. 65 (t, J = 7.5 Hz, 4H), 2.92 (quint, J = 4.6 Hz, 2H), 1.95-2.00 (m, 4H). 0.96 (t, J = 6.9 Hz, 6H)

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and evaluation of electrochromic display element] was performed to prepare an electrochromic display element using the compound (56) of the structural formula (56) as a coloring dye.

[Coloring and decoloring test 16]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

[Example 17]
<Synthesis of Electrochromic Compound (57) [Structural Formula (57)]>
<a> Synthesis of Intermediates (57-1, 57-2)

  The reaction and purification were carried out in the same manner as in Example 14 except that n-butyl bromide in step 14 (b) above was changed to 2,2,2-trifluoroethyl trifluoromethanesulfonate, and an intermediate (57-2) was obtained. Got). Yield 217 mg, 59%.

<C> Electrochromic Compound [Synthesis of Structural Formula (57)

A reaction and purification were performed in the same manner as in Example 14 except that the intermediate (57-2) was replaced with the intermediate (57-2) in place of the intermediate (31-2) in the step of Example 14 (c) to obtain the desired product. Yield 198 mg, yield 96%.
¹ H NMR (500 MHz, CDCl ₃ , δ): 9.29 (d, J = 6.9 Hz, 4 H), 8, 89 (s, 1 H), 8. 85 (t, J = 7.5 Hz, 8 H), 8. 64 (d, J = 8.0 Hz, 2 H), 8. 40 (d, J = 9.2 Hz, 4 H), 7.52 (d, J = 8.5 Hz, 2 H), 5.84 (q, J = 8.6 Hz, 4 H), 2. 92 (quint., J = 4.6 Hz, 2H), 1.88-1.95 (m, 2H)

[Preparation and Evaluation of Electrochromic Display Element]
In Example 1, the same procedure as described in [Preparation and Evaluation of Electrochromic Display Element] was performed to prepare an electrochromic display element using Compound (57) of Structural Formula (57) as a coloring dye.

[Coloring and decoloring test 17]
The absorption spectrum was measured in the same manner as in [Coloring and decoloring comparison test 1]. Absorption spectra in the bleached state and the colored state are shown in FIG. In the decolored state before voltage application, it was transparent without absorption in the entire visible region of 400 nm to 700 nm. When a voltage of -1.5 V was applied using a potentiostat (BAS Co., Ltd. ALS-660C), a black color developed.

(Result Summary)
As shown in FIGS. 4 to 21, from the absorption spectrum results of the decolorized state of the compound, in the comparative example, there was absorption in the visible region and yellow coloring was found, but in Examples 1 to 17, in the visible region It was confirmed that it had no absorption and was colorless. Furthermore, it was also confirmed from the absorption spectrum of the colored state that it was a black-colored electrochromic compound having absorption over the entire visible range. These results are also clear from the color value measurement results.
From this result, a high contrast light control element was produced by using the electrochromic compound according to the present invention.

JP, 2006-267829, A JP, 2011-102287, A

Claims (11)

An electrochromic compound represented by the following general formula (I).
(X _{1 to} X _{4 in} the general formula (I) represent the following general formula (II), or an alkyl group, an aromatic hydrocarbon group, or a hydrogen atom, and two or more of the X _{1 to} X ₄ are (Wherein a combination of X ₁ and X ₃ is excluded), the alkyl group and the aromatic hydrocarbon group are a halogen atom, an alkyl group, an aromatic hydrocarbon It may have a group selected from a group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group and a silanol group.)
(In General Formula (II), R _{1 to} R ₈ each independently represent a hydrogen atom.
B represents an alkyl group or an aromatic hydrocarbon group, and the alkyl group and the aromatic hydrocarbon group are a halogen atom, an alkyl group, an aromatic hydrocarbon group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, It may have a group selected from silyl group and silanol group.
A ^- represents a monovalent anion. m is 0-3. When there are a plurality of groups having the structure of the general formula (II), R _{1 to} R ₈ , B and m may be each independently different. ) The electrochromic compound according to claim 1, wherein three of X _{1 to} X _{4 in} the general formula (I) are represented by the general formula (II). Electro according to claim 1, wherein the substitution position of the general formula (II) is any _{two of} X ₁ , X ₂ and X _{4 in} the general formula (I). Chromic compound. An electrochromic compound represented by the following general formula (III).
(In the general formula (III), X ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or an aromatic hydrocarbon group, and the alkyl group and the aromatic hydrocarbon group are a halogen atom, an alkyl group, an aromatic hydrocarbon It may have a group selected from a group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group, and a silanol group.
R _{19 to} R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group, a silanol group or a cyano group, and the alkyl group is a halogen atom May be included.
R ₁₁ to R ₁₈ and _R 24 _{to R 31} represents a hydrogen atom independently.
Each of B ₁ and B ₂ independently represents an alkyl group or an aromatic hydrocarbon group, and the alkyl group and the aromatic hydrocarbon group are a halogen atom, an alkyl group, an aromatic hydrocarbon group, a phosphonic acid group, It may have a group selected from phosphoric acid group, carboxylic acid group, silyl group and silanol group. A1 ^-, and A2 ^- each represent a monovalent anion. m and n are each independently 0, 1, 2 or 3. ). An electrochromic compound characterized by being represented by the following general formula (IV) or the general formula (V);
(In the general formulas (IV) and (V), X ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or an aromatic hydrocarbon group, and the alkyl group and the aromatic hydrocarbon group are a halogen atom, an alkyl group And a group selected from an aromatic hydrocarbon group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group, and a silanol group.
R _{19 to} R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aromatic hydrocarbon group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group, a silanol group or a cyano group, The alkyl group may have a halogen atom.
R ₁₁ to R ₁₈ and _R 24 _{to R 31} represents a hydrogen atom independently.
Each of B ₁ and B ₂ independently represents an alkyl group or an aromatic hydrocarbon group, and the alkyl group and the aromatic hydrocarbon group are a halogen atom, an alkyl group, an aromatic hydrocarbon group, a phosphonic acid group, It may have a group selected from phosphoric acid group, carboxylic acid group, silyl group and silanol group. ^{A1 -, A2 -, A3 -} , and A4 ^- each represent a monovalent anion. m and n are each independently 1, 2 or 3. Y contains at least one methylene group, and may contain an alkyl group or an aromatic hydrocarbon group. ). The electrochromic compound according to any one of claims 1 to 5, which is any one of compounds represented by the following structural formulas (1) to (80).
The following structural formula (19), (27), (31), (35), (36), (37), (38) (42), (44), (50), (51), (56), The electrochromic compound according to any one of claims 1 to 6, which is any of the compounds represented by (57), (78), (79), and (80).
  An electrochromic composition having a structure in which the electrochromic compound according to any one of claims 1 to 7 is bonded or adsorbed to metal oxide fine particles.   The electrochromic composition according to claim 8, wherein the metal oxide fine particles are titanium oxide fine particles.   A display electrode, a counter electrode provided opposite to the display electrode at a distance from the display electrode, and an electrolyte disposed between both electrodes, at least any one of claims 1 to 7 on the surface of the display electrode. A display device comprising the electrochromic compound according to claim 1 or the electrochromic compound and the electrochromic composition according to claim 8 or 9.   A display electrode, a counter electrode provided opposite to the display electrode at a distance from the display electrode, and an electrolyte disposed between both electrodes, at least any one of claims 1 to 7 on the surface of the display electrode. An electrochromic compound according to claim 1 or the electrochromic compound and the electrochromic composition according to claim 8 or 9, characterized in that the display electrode, the counter electrode, and the electrolyte are transparent. Light control element.