WO1991002723A1 - Phenanthroline derivative, bipyridyl derivative, and electrochromic display element - Google Patents

Abstract

Derivatives of phenanthroline and bipyridyl each having a substituent which is capable of undergoing electrolytic deposition or electrolytic polymerization to be directly formed into film. They can be used in producing electrochromic display elements and so forth.

Description

 Specification

 Phosphorus derivatives, biviridyl derivatives, and electrochromic display elements

 Technical field

 TECHNICAL FIELD The present invention relates to a novel phenol-opened derivative and a vividyl derivative, and an electrochromic display element using the same. More specifically, the present invention can be used for various indicators, display elements, recording elements, and the like, and in particular, is applied to an electronic aperture display element and a photochromic display element. The present invention is directed to a suitable phenylene-containing phosphorus derivative and a bipyridyl derivative and an electrochromic display device using the same.

 Background art

Electro-chromic display devices (ECDs) have a reversible change in color and light transmittance due to a redox reaction that occurs at or near the electrode surface when a voltage is applied. This is a display element that utilizes the “romatic phenomenon”. The electronic aperture element is a non-emissive display element similar to the liquid crystal display, and includes a light emitting diode, a fluorescent display tube, an electronic luminescent element, and a plasma element. Low compared to light-emitting display devices such as displays and CRTs! ; Low-power consumption, low-power consumption, easy-to-read display, and memory function not found in other displays. The base density is lower than that of liquid crystal using photons. Good contrast, no viewing angle dependence, easy to see It has the following features.

 The electrochromic material used as a display pole or a counter pole of the electronic microdisplay element is used for the display stability and display of the electrochromic display element. It is an important factor because it affects diversification.

 On the other hand, it is known that phenanthine-containing phosphorus and viviridyl easily form coordinate bonds with various transition metal ions to form stable metal complexes. It is also known that the complex exhibits a unique color depending on the type of metal ion. In particular, these compounds are known as qualitative and quantitative reagents for iron divalent ions because they form a complex with iron divalent ions quantitatively and show a bright red color. Furthermore, these compounds form a colorless complex with iron (III) ion, and in addition, the reactions shown in the following formulas (I) and (Π) are electrochemically reversible. It is also used as an electrochromic material.

(Fe (summer) (Phen) 3) ^{2 +}

 Red one e

<― (Fe ⁽¹ ) (phen) 3)

 e colorless (

(In the formula, (phen) represents a phenanthine ring.) (Fe <I) (bpy) 3)

 Red one e

(Fe ^(I) (bpy) 3

 e

 Colorless I)

(In the formula, (bpy) represents vinyl.)

 At this point, such a phenanthroline-portion metal complex and a biviridyl metal complex are easily dissolved when they come into contact with a liquid, so that it is difficult to form a film. For this reason, when these metal complexes are used, for example, as an electrochromic material, a solution of these metal complexes is sealed between the electrodes, or a high molecule traps these metal complexes. This composite polymer must be fixed to the electrode to form an ECD cell.

 However, solution-type ECDs have extremely slow response speeds because the diffusion of the reactant, that is, the phenanthine-containing phosphorus metal complex or the biviridyl metal complex, in the solution is a rate-determining step. Become . On the other hand, ECD in the form of being trapped in a polymeric matrix such as polyacrylic acid or polyvinylamine hydrochloride can prevent the diffusion of these metal complexes, but can reduce the number of metal complexes that are the color-forming centers. Depends on the positive charge on the polymer, so the thickness must be increased to obtain sufficient color. Since polymers have inherently high insulating properties, an increase in film thickness causes a reduction in response speed and causes color unevenness such as remaining disappearance.

In addition, during the electropolymerization of conductive polymers such as polypyrrole, In addition, a method has been proposed in which a phenanthine-containing phosphorus metal complex is incorporated as a dopant. For example, Japanese Patent Application Laid-Open No. 60-188931 discloses that poly (pyrrol) formed by electrolytic polymerization of pyrrole incorporates iron-baso-phenanthine linsulfonic acid. The extreme is disclosed. However, since the conductive polymer itself is colored, the one formed by these methods has a problem in that the color change of the ECD is hindered, so that it can be used as a display element. . For example, polypyrrole-polyvinyl is black.

 Further, as another method of forming a display electrode by an ion complex of a polymer cation and a complex anion, for example, Japanese Patent Application Laid-Open No. Sho 62-10891 discloses A display electrode using an ion complex of a perfluorocarbon polymer having a quaternary ammonium salt in a lab chain and a phosphorus-sulfonic acid complex of iron-basophenanth opening is disclosed. However, each of the display electrodes disclosed in Japanese Patent Application Laid-Open Nos. Sho 60-188931 and JP-A-62-14891 basically uses polymer cations. Since it is composed of an ion complex of complex anion, the complex which is a coloring / decoloring agent may be eluted, and the durability and display quality of the electrochromic display element are reduced. The problem remained.

From this point of view, it is highly desirable to directly form a film of a phenanthrene-containing phosphorus metal complex and a biviridyl metal complex without using a carrier such as a polymer in producing an ECD. It was to be absorbed.

 Disclosure of the invention

 SUMMARY OF THE INVENTION An object of the present invention is to provide a novel phenene-opened phosphorus derivative and a viviridyl derivative, and an electrochromic display element using the same. The present invention can also be used for various indicators, display elements, recording elements, and the like, and is particularly suitable for use in electoric aperture display elements and photochromic display elements. It is an object of the present invention to provide a novel phosphorus-containing phosphorus derivative and a bipyridyl derivative, and an electrochromic display device using the same. The present invention further provides a novel phenanthroline derivative and a biviridyl derivative capable of forming a film by electrolytic deposition when a metal complex is formed, and an electrocycle using the same. It is an object of the present invention to provide a liquid crystal display element. It is still another object of the present invention to provide an electronic-original-chromic display element in which the color change at the display electrode is clear, and which is excellent in both durability and display quality.

In order to achieve the above object, the present invention provides a phosphorene derivative having a 1,10-phenylene derivative.

 9 10 1 2

At least one of the positions 3 to 8 is substituted with one of the following functional groups R.

R: -C00H, -R'-COOH (where R 'is "(~ C H 2— n

 -C H 2 n S-, s ~ c H 2 n-1 s-

One C O N H—, one C O O—, one C O—

— ^ OV- SO 2 N HfC H 2H- SO 2 N H-ec H 2 + _n ,

SO 2 NH,-SO 2 NH or 1 O—

 n is an arbitrary natural number. )

 In addition, the electronic aperture display device of the present invention can be formed on a transparent electrode by polymerizing a metal complex having the above-described phenanline phosphorus derivative as a ligand by an electrolysis method. This is used as a display pole or a counter pole.

Alternatively, in order to achieve such an object, the phenanthroline derivative of the present invention is a 1,10-phenanthrothine derivative.

At least one of the positions 3 to 8 is substituted with any one of the following functional groups R.

R

 (Where R 'is "CH2H ~ n

 -f-C H 2-)--S

n-S-CH ₂ -one

 Hi s —,

- ^ C ^ -. One - SS OO 33 -, - S 0 2 - one CONH-, one COO-, one CO-,

— <0) ~ SO 2 N H + CH 2+ _n ,

-SO 2 NH ~ fCH 20 _n ,

 — (0> —SO 2 NH, -SO 2 NH or 1 O—, and n is any natural number.)

In addition, the electoric-chromic display element of the present invention comprises an electrolytic polymer comprising a metal complex having the above-mentioned phenanthroic phosphorus derivative as a ligand. A film is formed on a transparent electrode by polymerization by a legal method, and this is used as a display electrode or a counter electrode.

 Furthermore, in order to achieve the above object, the biliyl derivative of the present invention is a 2,2′-biviridyl compound.

 4 3 3 '4'

At least one of the 3-5 or 3'-5'-positions of any of the following functional groups R is g-substituted.

 R: -C00H, -R '-C00H, (where R' is

Ten CH2 + _n , CH2 "^ S

One SCH ₂ + _n , one S-

, 鲁,

-S 03 one,-S 02 one, one C 0 N H—,

One C O O—, one C O—, or one 0—, and n is any natural number. )

 In addition, in the electric-port-mix display element of the present invention, a metal complex having the above-described bipyridyl derivative as a ligand is polymerized by an electrolytic deposition method to form a film on a transparent electrode, and the display is performed. They are intended to be used as poles or counter poles.

Alternatively, the bipyridyl derivative of the present invention comprises 2,2′-bipyridyl 3 '

At least one of the positions 3 to 5 or 3 ′ to 5 ′ is substituted with any of the following functional groups R:

 (Where R 'is ten C H 2 n

 One s — ゝ

 ,

— C O N H—, one C O O—, one C O—, or

— O—, where n is any natural number. )

 In addition, the electronic aperture display device of the present invention is characterized in that a metal complex having the above-described bipyridyl derivative as a ligand is polymerized by an electrolytic polymerization method to form a film on a transparent electrode, and this is displayed. They are intended to be used as poles or counter poles.

As described above, according to the present invention, electrolytic deposition or electrolytic polymerization can be performed on the phenolic skeleton and the viviridine skeleton. With the introduction of such functional groups, metal complexes having these derivatives as ligands can be easily prepared by electrolytic deposition or electrolytic polymerization without using a carrier such as a polymer. It can be fixed on the electrode. Further, the metal complex thus formed is

When used as an EC material, it can be formed directly on the electrode by electrolytic deposition or electrolytic polymerization without the need for an indispensable polymer or colored conductive polymer. As a result, the response speed is fast, and there is no problem such as color unevenness, and a clear display can be obtained by the change in the discoloration of the original EC material.

 BRIEF DESCRIPTION OF THE FIGURES

 Fig. 1 19.4 and "19.5-8; 9.5 £>" are a series of reaction process diagrams from the synthesis of the compound according to the present invention to the formation of a metal complex having the compound as a ligand.

 Fig. 6 is a sectional view showing an example of the structure of the electrochromic display element according to the present invention.

 Fig. 7 is a diagram showing a cyclic voltammogram of a film formed by depositing an iron-baso-nanto-port-line complex electrolytic polymer on the ITO electrode of the electrochromic display element according to the present invention. is there .

 Fig. 8 is a diagram showing the potential dependence of the electron spectrum of the iron-baso-phenanthine phosphorus complex electropolymerized membrane.

BEST MODE FOR CARRYING OUT THE INVENTION The phosphorus-containing phosphorus derivative according to the first aspect of the present invention is a 1,10-1 phosphorus-containing phosphorus derivative. 6 5

 At least the first position g of 3-10 in 9 10 1 2 has a functional group R capable of electrolytic deposition introduced.

 Such a functional group R may be a group having a carboxylic acid group at the terminal. Even if this carboxyl group is directly bonded to the phenolic ring as the functional group R, or it may be an alkyl group. Carbon (about 1 to 12 carbon atoms), oxygen (ether bond), sulfur (thick ether bond), ester bond, amide bond, sulfon bond, sulfin bond, sulfon ester bond, sulfon It may be bonded to a phenanthine-containing ring via a thioamide bond, a phenyl group, a ketone group, or the like, or a combination thereof.

 Therefore, the functional group R is, specifically,

R: -C00H, -R'-C00H,

(However, wherein R, is "CH 2 ten _n

-CH ₂ --,-S + CH 2 + S

 n, one,

〇>-, -S03-I, -S02-I

 C O N H —, one C O O —, one C O S 02 N ri— {-C H 2-„

一 S 0₂ N H- C H 2+ _n 、

One S 0 ₂ N H- CH 2+ _n ,

 ― S O 2 N H, one S O 2 N H or

— O—, where n is any natural number. Of these, preferably C H 2 ^-^ C 00 Η,

One S—C 00 H,-S-f C H 2-— O O H,

— (C ^ —COOH).

 The site to which these functional groups R are bonded may be at any position other than the 2-position and the 9-position, and the number (n) may be any number from 1 to 6; The number is 1 to 2 and the binding site is at position 4 and 7,

 Such phenolic phosphorus derivatives of the present invention are all known compounds such as 1,10-phenylene-containing or 1,10-phenylene-alkyl-substituted compounds. It can be obtained by organic chemistry synthetically using any known phenene-opened phosphorus derivative as a starting material.

 That is, first, 1,10-phenylene-open-line-5-carboxylic acid having one COOH group as a substituent R is 1,10-phenylene-open-line-15-methyl aromatic. It is obtained by oxidation of a methyl group which is a group III chain.

Also, 1, 10 — phenanthine phosphorous-3-carboxylic acid is It is obtained by the oxidation of 1,10-phenylen-3-methyl.

C00H

 In addition, 1,10-phenylene-l-butyric acid is obtained by oxidation of 1,10-phenylene-l-l-methyl.

次に置換基 R と して 一 C O O H基を 2つ有する 1 , 1 0 一 フエナン ト 口 リ ン一 4 ， 7 —ジカルボン酸は 4 ， 7—ジ メチルー 1 , 1 0 — フエナン ト口 リ ンのメチル基の酸化に よ って得られる 。 H ₃ C H00C

Next, the 1,10-phenylene-containing 1,4,7-dicarboxylic acid having two COOH groups as substituents R is 4,7-dimethyl-1,1,10-phenylene-containing phosphorus. Obtained by oxidation of a methyl group.

In addition, 1,10-phenylene-open-line-5- 5-acid having one CH 2 COOH group as a substituent R is 5-methyl-110-methyl-line of phenyl-openin Then, sodium metal is reacted in an inert gas atmosphere to produce 5-methyl-1,10-l-nanopentium sodium, which is then treated with carbon dioxide. Obtained by the action of hydrogen and further hydrolysis. In addition, derivatives having different substitution positions of one C H2 C 0 OH group can be obtained by the same dilation.

 In addition, 1,10-phenanthroline having 1,2-CH4COOH as a substituent R is 1,4,7-diacetic acid is 4,7-methyl-1,10-phenanthroline. Reacts with sodium metal in an inert atmosphere to produce 4,7-methyl-11,10-l- linitina sodium at the phenantine port, which is acted upon by carbon dioxide and further hydrolyzed. Obtained by decomposition. In addition, derivatives having different substitution positions can be obtained in a similar manner. The phosphorus derivative of the present invention according to the second aspect of the present invention is a 1,10-phenylene derivative.

 9 10 1 2

In at least one of the 3 to 8 positions, a functional group R capable of electrolytic polymerization is introduced.

Such a functional group R may be any one having an electropolymerizable aniline pyrrole, thiophene, franne, hydroxyphenyl group or the like at the terminal. Even if the functional group R is directly bonded to the phenyl ring, the alkyl group (about 1 to 12 carbon atoms), oxygen (Ether bond), sulfur (thioether bond), ester bond, amide bond, sulfon bond, sulfin bond, sulfon ester bond, sulfonamide compound, phenyl group, ketone It may be bonded to the phenanthine-containing ring via a group or the like, or further via these combinations.

 Therefore, the functional group R is, specifically,

0H

0H

(Where R 'is "CH2n

-f CH 2--n S-S + CH 2+ _n , one S-,

 ~ ^ (O-S O 3-,-S O 2-,

One C O N H—, one C O O—, one C O—

 S O 2 N H + C H 20

n、

n,

-S O 2 N H-f C H 2 + n,

0> —S 0 ₂ NH, 1 SO 2 NH or 1 O—, and n is an arbitrary natural number. )

It is expressed as Of these, NH ₂ is preferred.

The binding site of these functional groups R is Any number of rice plants may be used, and the number “n” may be any number from 1 to 6; however, the number is preferably from 1 to 2 as in the case of the first aspect. The binding sites are at positions 4 and 7.

 Such a funnel-opened derivative according to the second aspect of the present invention is a known compound, as in the case of the above-described first aspect, and is a 1,10-phenanthone-opened compound. It can be obtained by organic chemistry synthesis using a known phenantine-containing phosphorus derivative such as phosphorus or a 1,10-phenylene-containing phenylalkyl-substituted product as a starting material.

H ₂ 基を有する 1 ，For example, for the substituent R

1 having an H ₂ group,

10—The phenanthine mouth derivatives are prepared by converting the carboxyl group to an acid chloride with thionyl chloride, and then phenylenediamine, preferably o—at least one of the phenylenediamines. Obtained by reacting with a mino group to form an amide bond

 Further, when the substituent R is ~ i) ~ -SO2NHC

Bis (o-hydroxybenzylaminosulfonyl), which has two amino acids, reacts with sodium pentachloride Thus, bathophenanthrin sulfonyl chloride is obtained, which is obtained by reacting this with a primary amine having a phenol group. On the other hand, the viviridyl derivative according to the third aspect of the present invention is also 2, 2'-viviridyl.

4 3 3 '4'

At least one of the positions 3 to 5 or 3 'to 5' of the above has a functional group R (-C00H, -R'-COOH) capable of electrolytic deposition as described above.

 Further, the site to which the functional group R capable of electrolytic deposition is bonded may be at any position other than the 6-position and the 6′-position, and the number “n” may be any number from 1 to 6 However, preferably, the number is 1 to 2 and the binding sites are at positions 4 and 4 ′. All such viviridyl derivatives according to the third aspect of the present invention are known. A known compound such as a 2,2′-biviridyl or 2,2′-viviridylalkyl-substituted compound can be obtained as a starting material by organic chemical synthesis. You.

 That is, first, as a substituent R, —4-carboxy-2,2 · —biviridyl having one C 00 H group is a methyl group of 4,4-dimethyl-2,2′-biviridine. One of

Obtained by oxidizing with K M n 04

4,4'-Carboxy-1,2,2, -biviridyl having two COOH groups as substituents is 4,4,1-dimethyi. Rou 2,2'—Obviridyl is obtained by oxidation of the methyl group, which is the aromatic 111 chain.

 Furthermore, the biviridyl derivative according to the fourth aspect of the present invention is also a 2,2′-biviridyl derivative.

4 3 3 '4'

In at least one of the 3 to 5 or 3 'to 5' positions of the electropolymerizable functional group R (aniline, pyrrole, thiophene, furan, t (Doxyphenyl group).

 The site where the functional group R capable of electrolytic deposition can be bonded may be at any position other than the 6-position and the 6′-position, and the number (n) may be any number from 1 to 6 But preferably the number is 1-2 and the binding sites are at positions 4 and 4 '

The bipyridyl derivative according to the fourth aspect of the present invention is also a known compound 2,2′-bibi, similarly to the bipyridyl derivative according to the third aspect. A known biviridyl derivative such as a benzyl or 2,2′-biviridylalkyl-substituted product can be obtained as an organic chemical synthesis starting material. For example, as a substituent,-one CC OO NN HH ^N ~~ ^H2 V (([, (4,4'-bis (aminoanilinocarbonyl) having two groups having two groups) 1, 2,2 ¹ one Bibi lysine is 4 were synthesized cormorants I above, 4 '- Jikarubokishi 2, 2' are heated with trichloride Li down five Li emissions chloride or chloride Chioniru an Bibi lysine 4, 4 The carboxyl group at the 'position is acid-halogenated and further ripened with phenylenediamine to replace the C jg of the acid chloride group at the 4,4' position with phenylenediamine. It is obtained by

 As described above, the phenanthroline derivatives and the viviridyl derivatives according to the first to fourth aspects of the present invention are all 1,10-phenanthroline-derived and 2,2-biviridyl. Similarly, it easily coordinates with various transition metals to form a complex.

 Furthermore, since these complexes cause reversible oxidation / reduction reactions accompanied by discoloration by changing the applied voltage, they can be applied as electrochromic materials.

 That is, the phosphorus derivative and the biviridyl derivative are represented by the following formulas (m) and (IV), respectively.

(M (phen- R „) 3) X _m (I)

(M (bpy-R ») 3) X _m (IV)

(Wherein, M is a transition metal, X is a counter anion, phen is 1,10-phenanine-containing phosphorus, bpy is 2,2′-biviridyl, and R is Enables such electrolytic deposition Functional radical, n shows a number of functional groups, and m is a variable ranging from 0 to 6, respectively _[Phi)

Forms a metal complex represented by

 Here, the transition metal serving as the central element is not particularly limited, and various ones can be applied. In particular, F e, C o, N i,

Cu, Zn, Cr, Mn, Hu, Cd or Os can be mentioned as preferred. Also, various types of negative ions such as CJI-I, CJ104 ", N03", I ", and Br" are applied.

 Thus, such a metal complex having a ligand of a phenantine-containing phosphorus derivative or a biviridyl derivative according to the present invention is characterized in that the phenantine-containing phosphorus derivative or the biviridyl derivative has a specific functional group as described above. Since R has a molecular structure, film formation by electrolytic deposition is possible.

 Here, the electrolytic deposition means that a certain substance dissolved in an electrolytic solution is deposited on an electrode by an electrochemical reaction on an electrode, and includes, for example, electrolytic plating, electrolytic polymerization, and the like. It is.

For example, Fig. L shows a series of processes from the synthesis of a phenanthroline derivative having a CH 2 COOH group at the 4- and 7-positions as the functional group R to the film formation by electrolytic deposition of its iron (Π) complex. This shows the reaction process. As is evident from this reaction step, if a substituent having a terminal COOH group is present in 1,10-phenanthroline or 2,2'-biviridyl, for example, Electrolytes such as C a CJ! 2 and C a (C jg O ₄ ) 2 can be used, for example, with N, N'-dimethylformamide (DMF), N-formamide, formamide, dimethyl sulfoxide (DMS 0 ), Tetrahydrofuran (THF), acrylonitrile, acetonitril, butyronitrile, propylene carbonate, 1,2-jetroxetane, dichloroethane down, two preparative Roeta down, the electrolytic solution comprising a polar solvent such as pyridinium gin, dissolved metal饍体of the derivative as a ligand, if the reduction on the electrode, one COO ^e C a ® _4, which is formed into a film by Oko the by that cross-linking to Yo I Do Lee on binding of ^e OOC-

Fig.2 has _two CONHH groups as functional groups.

Fig. 3 shows a series of reaction steps from the synthesis of the phenolic derivative at the 5-position to the growth of the iron (II) complex by electrolytic deposition. This section shows a series of reaction steps from the synthesis of a biviridyl derivative having a ^ —NH 2 group at the 4 and 4 'positions to the formation of the iron (II) complex by electrolytic deposition.

 As is evident from this, the 1,10—final mouth ring or 2,2

 -C 0 NH ~ <^-"When a substituent having an NH 2 group is present, a metal complex having such a derivative as a ligand is dissolved in the electrolyte and oxidized on the electrode. The substituted aniline group causes a condensation reaction between the complex molecules, and a film is formed.

The electrolyte used for this growth is, for example, Alkali metal salts such as KC j ?, alkali metal perchlorates such as LiCί4, and perchlorines such as tetraethylammonium perchlorate (hereinafter referred to as Τ Ε Α) A commonly used electrolyte such as a tetraalkylammonium acid salt is dissolved in a polar solvent as described above.

 Figure 4 shows the results of the synthesis of a phenanthroline derivative having a single COO "~ <^-" 0H group at the 5-position as the functional group R, and the formation of the iron (II) complex by electrolytic deposition. 1 shows a series of reaction steps up to a membrane. As is clear from this, when a substituent having a C 0 O ~~ (Q ^ —OH group is present at the terminal of 1,10-phenanthroline or 2,2'-biviridyl, However, when a metal complex having such a derivative as a ligand is dissolved in an electrolyte and oxidized on an electrode, the substituted phenoxy group causes a condensation reaction between adjacent complex molecules to form a film. The electrolyte used for forming the film is, for example, an alkali metal salt such as KC £,

Commonly used electrolytes such as alkali metal perchlorates such as LiC & 04, and tetraalkylammonium perchlorates such as TEAP are dissolved in polar solvents as described above. is there

 Also, Fig. 5A-Fig. 5D shows that the functional group R

From the synthesis of phenanthine-containing phosphorus derivatives at positions 4 and 7 A series of reaction steps up to film formation by electrolytic deposition of the iron (II) complex is shown. In this case as well, as in the case shown in FIG. 4, the presence of a substituent having a phenoxy group at the terminal makes it possible to dissolve a metal complex having such a derivative as a ligand in the electrolyte. However, when oxidized on the electrode, this substituted phenoxy group undergoes a condensation reaction between adjacent complex molecules and is formed.

 Furthermore, in the case of other functional groups according to the present invention, the electrolytic deposition can be similarly performed, for example, having an “η 基 group at a terminal.

H

In the case of a metal derivative having a ligand such as a phenol-containing phosphorus derivative or a bipyridyl derivative into which a functional group R is introduced, the group is dissolved in an electrolytic solution and reduced or oxidized on an electrode to form the group.

₄ also is formed by being Ri polymerized by the oxidative polymerization, full Henin preparative functional group R having a group at the end has been introduced b Li

Metal complex having a ligand of a benzoyl derivative or a viviridyl derivative also dissolves in the electrolyte and oxidizes on the electrode.

基が電解酸化重合によ り高分子化して成膜化される 。 さ ら に、 末端に 基を有する官能基 Rが導入されたフ エ

The groups are polymerized by electrolytic oxidation polymerization to form a film. So Into which a functional group R having a terminal group is introduced.

In the case of a metal complex having a ligand such as a phosphorus derivative or a biviridyl derivative as a ligand, when dissolved in an electrolytic solution and oxidized on an electrode, the ij group is polymerized by electrolytic oxidation polymerization. It is formed into a film.

 The phosphorus-containing phosphorus derivative and the biviridyl derivative of the present invention are 1, 10- and phosphorus-containing derivatives, respectively.

2.2'—By introducing a specific functional group as a substituent into the viviridyl at a position that does not hinder complex formation, when a metal complex is formed, electrolytic deposition can be used. The metal complex of the present invention having a ligand of the phenylene-opened derivative and the bipyridyl derivative of the present invention can be formed by an electrolytic deposition method or an electrolytic polymerization method. In this case, an electoric chromic display element using this as an electoric chromic material is excellent in response speed and capable of forming a film on the electrode itself. Since the original color development and color elimination of the electrochromic material can be used, the visibility is excellent. Further, the phenanthrene-containing derivative and the biviridyl derivative of the present invention are particularly suitable for use in the above-described electoric chromic material, but include various indicators, display elements, recording elements, It can also be used for photochromic display elements.

Hereinafter, the present invention will be described in more detail with reference to Examples. FIG. 6 is a drawing showing a schematic structure of an embodiment of the electronic mouthpiece display device of the present invention. In the figure, 1 is a display electrode substrate, 2 is a transparent electrode, 3 is a peak, 4 is a display material, 5 is an electrolyte, 6 is a background plate made of filter paper, 7 is a transparent electrode, and 8 is a facing electrode. An electrode substrate, 9 is a counter electrode member, and 10 is a sealing material.

 In this embodiment, a film-like transparent electrode 2 is formed on a transparent display electrode substrate 1, and further, as a display material 4 on the transparent electrode substrate 1, the above-described fin opening according to the present invention is provided. Electron analysis of metal complexes with ligands of phosphorus derivatives and biviridyl derivatives, for example, tris (1,10-phenylene-1,4,7-dicarbonsan) iron (Π) The display electrode is formed by film deposition and lamination as described above.

 The portion of the transparent electrode 2 where the display material 4 is not laminated is masked by an insulating film 3 so that a display design can be obtained at a desired position, form, arrangement, or the like. .

 The display electrode substrate 1 is generally made of a transparent substrate such as glass or plastic. As the transparent electrode 2, a known conductive film material, for example, tin oxide (SnO 2), indium oxide (In 203) (IT 0>), etc., is used. An insulating material such as an epoxy-based insulating material is employed.

As the electrolytic solution 5 as an interelectrode material sealed between the supporting substrates 1 and 8, it is preferable to use an aqueous solution containing a known electrolyte such as calcium chloride (CaC £ 2). But limited to this The invention is also possible using other electrolyte or solid electrolyte instead ₄ as a solid electrolyte, print Lee Nki and also by Nda used for coating assembly formed was added in small quantities, its pro Bok emissions專It is preferable to employ one in which the properties are maintained and these layers printed or applied and cured are effective as a solid electrolyte layer of an electrochromic display. For example, as disclosed in JP-A-59-195629, titanic acid, stannic acid

_{(S n 02 · Χ Η 2} 0), antimonate _{(S b 2 0 3 · XH} 2 O or S b 2 05 · XH 2 0 ), zirconium acid

(Z r (0 H) 4 · Χ Η 2 0), is selected from niobate _{(N b 2 0 5 · XH} 2 O), tantalum acid (T a2 O 3 · XH 2 0> and Kei acid The main component is one or a mixture of two or more, and the binder is a polyhydric alcohol, water-soluble polymer or water-soluble polymer which is normally liquid at a steam pressure of 0.1 Hg or less at 20 Hg or less. Water or a water-soluble solvent such as a lower alcohol, a lower ketone, a lower ether, or the like was used as a solvent for the emulsion-type polymer to be further inked or formed into a coating composition. Use of things is preferred.

- How, opposite poles, as a _¾ opposing electrode member 9 and a counter electrode member 9 for being stacked on the transparent electrode 7 and further its is formed on the counter electrode substrate 8 Causes a reaction opposite to that of the display material 4 (that is, if the display material causes an oxidation reaction, a reduction reaction occurs, or if the display material causes a reduction reaction, an acid occurs. An EC material is used. For example, when tris (1,10-phenanthroline-1,4,7-diacetate) iron (（) is used as the display material 4, the counter electrode member 9 is oxidized in advance. The same amount of tris (1,10-phenanthine-line 1,4,7-diacetate) iron (IE) can be used. However, as the counter electrode member 9, it is not always necessary to use a metal complex having a ligand of the phenantine-containing derivative and the bipyridyl derivative according to the present invention, and a known material is used. In this case, for example, cobalt phthalocyanine (CoPc) @prussian blue (PB), which is stable in a reduction reaction, can be used.

 In order to receive a uniform power supply, the counter electrode member 9 is formed with a collector layer (not shown) of Ag, Cu, C, etc. on the counter electrode substrate 8 and formed thereon. It is preferable to coat. In particular, if a material that can be soldered, such as Cu or Ag, is used for the integrated layer, contact with the drive circuit becomes easy.

 As a sealing material, an ultraviolet-curable adhesive such as an epoxy-modified acrylate resin is used.

The oxidation reaction at the display electrode and the reduction reaction at the counter electrode exemplified in this embodiment are as follows. Display pole

(Fe ^{c 1} '(phen- Ac) 3) red one _e one

(Fe ^(, '(phen- Ac) 3) ^{3 +} e

 Colorless counter electrode

(Fe ^(I) (phen- Ac) 3)

― E

-(Fe ^(I) (phen- Ac) 3) ^{2 +} e

(Fe (') (Fe (CN) ₆ ))

Prussian blue e

<-(Fe ^(I> (Fe (CN) ₆ )) ² — e

 Prussian white e

CO ⁽¹ 'Pc (-2)): (Co ^(I Pc (-2)) ■

 e

Cobalt phthalocyanine

 (However, in the formula, phen represents a phenanthroline, Ac represents one CH2COOH, and Pc represents phthalocyanine.)

 The phenanthroline derivative of the present invention and the biviridyl derivative suitable for use in the electronic aperture display device were specifically obtained as follows.

Example 1 Functional group R: -C H 2 C O O H

4,10-Dimethyl-1,1,10—Fenanthate Lin As a ligand, a trisiron (II) complex chlorate

 (F e (phen (C H 2 C O H) 2) 3 ■ 2 C j¾ O 4) is synthesized. * This is suitable for use as a red E C material.

 I. Synthesis of tris (1,10 phenanthine mono-4,7-diacid) iron (Π) perchlorate

 1-1. Synthesis of 4,7-dimethyl-1,10-phenanthine

(1) First, a reflux condenser, a dropping funnel, and a rotor were set in three flasks, and the part was thoroughly dried while passing dry N 2 gas through ( _4).

 (2) Next, 10 ml of dry xylene was placed in a flask, and 0.69 g (3 × 10-2 raol) of sodium metal was added and ripened. When the sodium melted, it was stirred at a high speed to disperse the sodium. Thereafter, the mixture was allowed to cool rapidly, and xylene was distilled off.

③ Next, add 40 ml of n-hexane to the container and add ice

And cooled to an 1 5 ^e C in N a C £ solution. Their to, n -. § mill click Rorai de 1 8 3 ml (5 xl 0 - 3 lB0 l) e pressurized and Gently and stirred for 30 minutes.

④ 一 15 C drink or, 4,7 - dimethyl Chirufu Henin preparative port Li down 1 0 9 £. (5 X 1 0 - 3 liiol) and Te bets la methylethylene Zia Mi emissions 1 5 1 ml (lxl O - . 2 raol ) Was added over 10 minutes.

⑤After slowly returning to room temperature (20 to 30, preferably about 25), the mixture was stirred for several hours. The operation up to this point was all the lines of cracks in an atmosphere of nitrogen gas _¾

 1-2. Synthesis of 1,10-phenanthine 1,4-diacetic acid

(1) The 4 _: 7-dimethyl-1,10-phenanthrolinninatodium synthesized in the batch 1 was not isolated, but excess C02 gas was blown into the solution and allowed to stand overnight.

 ② After standing, 150 ml of distilled water was added and stirred. Since the eyebrows were separated, the water eyebrows were washed with hexane, benzene, and ethyl diester in this order, and unreacted substances were extracted and removed.

 (3) Finally, the reaction solution was adjusted to about PH 4 with 1 N—H C &, and the precipitate was collected by filtration and dried.

 赤 外 The precipitate was analyzed by infrared absorption spectroscopy (KBr method) and H—NMR (CDC £ 3). The presence of a carboxyl group in the molecular structure was confirmed.

 1-3. Synthesis of tris (1,10-phenylene 4,1-dinitrate) iron (II) perchlorate

① F e C £ ₂ · 4 H 20 and 1,10-phenanthroline-14,7-diacid obtained in 1-2 are combined with water or water-methanol ( 1: 1) The reaction was performed at a ratio of 1: 3 in the solution.

 (2) Then, excess NaCjg04 saturated aqueous solution was added. The resulting precipitate was collected by filtration, washed with cold water and ether in that order, and dried.

Growth of tris (1,10-phenanthine 4,7-diacid) iron (H) ① Application Benefits scan (1, 10 Fouesnant preparative port Li down one 4, 7 - Two acetic acid) obtained in I Iron (E) perchlorate 1> 1 0 - ³ 1101 / £ and 0 & (£ 2 An electrolyte was prepared by dissolving 0.1 mo I / JZ in acetonitrile, and this electrolyte was deoxygenated by N2 gas publishing.

 (2) Using a tin oxide or indium oxide (ITO) glass electrode as the working electrode, a platinum plate of the same area as the counter electrode, and a saturation force rommel electrode (SCE) as the reference electrode, and a current density of 5 to 10 iΑ / αδ A current was applied so that the IT0 electrode became the cathode, and force source electrolysis was performed. In this experiment, a constant current of 5 A / di was applied for 1 hour.

③ followed, the ITO electrode was washed with § Se Toni preparative drill air dried ₄

 I. Elect-mouth chromism of tris (1,10-phenanthine-line 1,4,7-diacetate) iron (Π)

 Cyclic voltammetry of the deposited electrode showed that at a scanning speed of 50 raV / sec, it was oxidized at +1.07 V (vs. SCE) and changed from red to colorless, It was reduced again at 0.68 V (vs. SCE) and turned from colorless to red. As the electrolyte, acetonitrile containing 0.5 M Ca (C £ O 4) 2 was used.

As is evident from these results, the electrode on which the tris (1,10-phenanthroline-14,7-diacetate) iron (III) complex was formed was a red-colorless electrochromic electrode. It was found that it could be used as a material. Example 2 Functional group: R—CONH (Fenantou

(Lin derivative)

 I. Synthesis of tris (5-(2-aminoaminolinocarbonyl)-1, 10-phenanthroline) iron (Π) complex

1-1. Synthesis of 5-Carboxy-1,10-phenanine Mouth Dihydrochloride

 ① First, 5-methyl-1, 10-phenanthine lin 0.5 ε

(2.6 X 10- ³ BO l) of water one pyridinium Jin (3: 1) was dissolved in a mixed solvent 4 in 0 ml.

② Next] CM n 04 0.62 g of (3.9 x 10- ³ nol) was added and 6 hours pressurizing ripe reflux with stirring.

③ Further, 0.62 _g of Κ ηθ4 dissolved in 10 ml of water was added, and the mixture was heated and refluxed for 12 hours while stirring.

 (4) The reaction solution was naturally filtered to remove the generated ηηθ2. Further, θηθ2 on the paper was extracted by washing with ripened water.

 The combined solution and washing solution were reduced to about 100 ml, and adjusted to about PH2 with hydrochloric acid.

 (4) After condensing to dryness using an evaporator, the mixture was extracted by boiling with ethanol.

 ⑦The ethanol solution from which insolubles had been removed was concentrated, and cooled in ice water while keeping the container.

(4) Hydrochloric acid gas was blown, and the resulting precipitate was collected on a G-4 glass filter. Wash the precipitate with hydrochloric acid-saturated ethanol And dried under reduced pressure.

The yield of precipitated 5- (1-carboxy) 1,10-phenanthine-linolenate was 0.2 g, and the yield was 29% ₄

1-2. 5—Synthesis of Carbo-Carbon 1 _: 1 10—Fenanthone Lin

Carboxy one 1, 10- Fouesnant collected by filtration Li down dihydrochloride 0 2 _ff a (6.8 X 10- ⁴ mol) was dissolved in chloride Chio sulfonyl 30 ml - ① the 1 - 1 synthesized in 5..

 ② Heat to reflux for 4 hours.

③ After cooling, the chloride Chioniru to Tome却, to狨圧dried ₄

 使用 Used for the next step without isolation.

 1-3. Synthesis of 5- (2-amino-2-linocarbonyl) -1,1,10-phenanthroline

 (1) 10 ml of dehydrated pyridine was added to a vessel containing 1,10-phenanthine-lin-5-carboxylic acid chloride synthesized in 1-2 to dissolve the contents.

② o - went phenylene Renjia Mi emissions ^{0.15 g (1.4 x 10- 3 raol} ) stirred added dissolved However the pin lysine solution (20ml) in the vessel while pressurized ripening refluxed for 1 2 hours.

 (3) After the reaction solution passed naturally, the solution (4) was reduced to about 5 ml. Excess ether was poured into the mixture, and unreacted o-phenylenediamine was removed, and the resulting precipitate was collected by suction.

④After drying, it was dissolved in water and made into alkaline by adding dropwise an INNaOH aqueous solution. This allows unreacted phena Except emissions Toro Li Nkarubon acid is the reaction product 5 - (2 - A Minoan two Li Bruno carbonyl) one 1, _beta was collected by浐過10-full Henin preparative port Li down Me沈濺

 残渣 The paper residue was thoroughly washed with distilled water and dried under reduced pressure. The yield of the product was 68.eg, and the yield was 32%.

When the obtained powder was subjected to infrared absorption analysis (KBr), it was found that 1650 on-1 (le c-.), 3200 on " ¹ (le _NH ) and ₃₄₀₀ cm -1 ( ( _NH ) each have an absorption peak, and 1 H-NMR (CDCI 3) analysis = 2.72 due to one CONH— and 3.7 due to S and one NH2. 2. The shift of S was observed, confirming the presence of an amide bond and an amino group in the molecular structure.

1 -4. Synthesis of tris (5— (2—aminoaminolinocarbonyl) -11,10—phenanthine) iron (II) perchlorate

(1) The 5-((2-aminoaminolinocarbonyl))-1,10-phenanthine obtained in 1-3. Was dissolved in chloroform and the insolubles were passed through.

 ② Concentrated to dryness with an evaporator.

 ③ The precipitate was dissolved in a small amount of dimethylformamide (DMF), and FeCi2.4H20 (bQag) was added.

 ④MU Ban (Agitated for about 1 hour while blocking light at about 2.

 DDMF was distilled off as much as possible without applying heat.

5 Add 50 ml of distilled water and excess to the _Fe complex N a C jg 04 was added.

 沪 The resulting precipitate was suctioned off and washed with a small amount of cold water.

®— 晚, dried under reduced pressure ₄

The yield of the obtained fin bodies was 68 mg.

 Tris (5-(2-aminoa 2 linocarbonyl) 1

1, 10—Fenantine Lin) Growth of iron (iron)

 (1) Tris synthesized in I (5— (2—amino-2-linocarbonyl) -1,1,10—phenanthroline) Iron (II) perchlorate

Was dissolved 1 X 10 one ³ nol / perchloric Sante preparative Rapuchi Ruan monitor © beam a (TBAP) O. lmol / jg in § Se Toni Application Benefits Le the electrolyte solution was adjusted. The electrolyte was deoxygenated by N 2 gas publishing.

 (2) Using ITO glass electrode for the working electrode, platinum plate of the same area for the counter electrode, and SCE for the reference electrode, passing a constant current of 20 A / d for 30 minutes so that ITO becomes the cathode. I did.

 (3) Thereafter, the ITO electrode was washed with acetone and air-dried.

 I. Tris (5-(2-aminoa-di-carbonyl)-1,10-phenanthine) Electric mouth chromium of iron (copper)

Cyclic voltammetry of the deposited electrode showed an oxidation peak at a scanning speed of 50 mV / sec at 10 V (vs. SEC) and a rededuction peak at +1.05 V (vs. SEC). And the Fe complex clearly reacts Example 3 in which this was confirmed that the functional group RCONH (bipyridyl derivative

Conductor>

I. Synthesis of tris (4, 4-bis (aminoanilinocarbonyl)-12, 2 '-pyridine) iron (copper) complex

1-1.Synthesis of 4,4'-dicarboxy-2,2'-biviridine dihydrochloride

 ① 4,4'-Dimethyl-2,2, -Viviridine 0 · 48 s

(2.6 X 10- ³ ηιοΙ) Water - pin lysine (3: 1) was dissolved in a mixed solvent 4 in 0 ml.

_{② KM n 0 4 1.24g (7.8} x 10 "3 ιιοΙ) and the mixture was stirred at reflux with a reluctant 6 hours pressurized ripening.

③ Further, 1.24 _ff of KMn04 dissolved in 10 ml of water was added, and the mixture was heated and refluxed for 12 hours while stirring.

 (4) The reaction solution was naturally filtered to remove the generated ηηθ2. Furthermore, Μηθ2 on the paper was extracted by washing with ripened water.

 ⑤ The combined solution and washing solution were concentrated to about 100 ml, and adjusted to about PH2 with hydrochloric acid.

 濃縮 After concentrating to dryness with an evaporator, it was extracted by boiling with ethanol.

 (4) The ethanol solution from which insolubles had been removed was concentrated and cooled in ice water while keeping the container.

⑥Hydrochloric acid gas is blown, and the resulting precipitate is Collected on Luther. The precipitate was washed with ethanol saturated with hydrochloric acid and dried under reduced pressure.

 1-2. Synthesis of 2,4'-bicarbyl 2,4'-biviridine

 ①4, 4 'synthesized in 1-1 above.

2, 2, was dissolved one Bibi lysine dihydrochloride 0.21 g of (6.8 X 10- ⁴ no I) to Ji old sulfonyl 3 0 ml chloride.

 ② Next, the mixture was heated and refluxed for 4 hours.

 (3) After standing to cool, thionyl chloride was distilled off and (2) pressure-dried.

 使用 Used for the next step without isolation.

 1-3. Synthesis of 4, 4 '-bis (2-amino-linocarbonyl) -2,2'-bibiridin

 (1) 4, 4 'dicro-carbone synthesized in 1-2

 2, 2 '— 10 ml of dehydrated pyridine was added to a viviridine container to dissolve the contents.

(2) o—Pyridine solution (20 ml) in which 0.22 g (2.0 × 10 " ³ ιηο I) of phenylenediamine was dissolved was added to the container (2), and the mixture was heated and refluxed for 12 hours while stirring.

 (3) After the reaction solution passed naturally, the solution was reduced to about 5 ml. Pour excess ether into it and unreacted o-! A precipitate formed while removing nigrenamine was collected by suction filtration.

④After drying, it was made alkaline by dissolving it in water and dropping an aqueous solution of INNaOH, thereby removing the unreacted phenolic carboxylic acid at the phenolic opening. 4,4'-bis (2-aminoaminocarbonyl) one

Collected via precipitation of 2, 2'-bibiridin.

残渣 The paper residue was thoroughly washed with distilled water and dried under reduced pressure.

1-4. Synthesis of tris (4,4'-bis (aminoinolinocarbonyl-2,2'-bibiridin) iron (E) perchlorate

① 4, 4'-bis (2-aminoaminolinocarbonyl)

2, 2'-Viviridine was dissolved in black-mouthed form and the insoluble matter was removed.

 ② It was concentrated to dryness by an evaporator.

 (3) The precipitate was dissolved in a small amount of DMF, and FeC £ 2.4H2O (50M) was added.

 撹 拌 The mixture was stirred at room temperature (about 25) for 1 hour while blocking light.

 DDMF was distilled off as much as possible without ripening.

 50 50 ml of distilled water was added. Then, an excess of NaC £ 04 was added to the Fe complex.

 ⑦ The resulting precipitate was suctioned off and washed with a small amount of cold water.

 ⑥Dry under reduced pressure overnight

 Film formation of tris (4, 4 'mono-bis (aminoanilinocarbonyl)-2,2'-viviridine) iron (copper)

① Bok synthesized in I Li scan (4, 4 '- bis (A Minoan two Li Bruno carbonyl) one 2, 2, One chatter Jin) iron ([pi) perchlorate 1 X 10 one ³ rao I / £ And perchlorate tetrapyl ammonium

(TBAP) O. lniol / £ was dissolved in acetonitrile to prepare an electrolyte. This electrolyte is used for N 2 gas publishing. More dehydrogenated.

 (2) An ITO glass electrode was used as the working electrode, a platinum plate of the same area was used as the counter electrode, and SCE was used as the reference electrode. A constant current of current density was applied for 30 minutes so that I T0 became the cathode.

 (3) Thereafter, the ITO electrode was washed with acetonitril and air-dried.

 I. Tris (4,4'-bis (amino-aminolinocarbonyl) —2,2, -Bibiridin> Electric mouth chromium of iron (Π)

 Cyclic voltammetry of the deposited electrode shows that when the scanning speed is 50 «V / sec, the oxidation peak is +1.1 V (vs. SEC) and the redox is +1.05 V (vs. SEC). A voltammogram having a peak was obtained, and it was confirmed that the Fe complex was clearly reacted.

Example 4

For the functional group R

 Bis (o-hydroxybenzylamino-sulfonyl) bis (enoxy) sulfonate is synthesized from sodium naphthyl sodium phosphate and sulfonate. To synthesize tris (bis o-hydroxybenzylaminosulfonyl) iron so- phenanthrin) iron (。), which is suitable for use as a red EC material.

I. Tris (bis (o-hydroxybenzylaminosulf) Onyl) no, 'sofenantine lin) Iron (E) synthesis

 1-1. Synthesis of soft-enhanced mouth disulfonyl chloride

① basophenanthroline Fenan preparative port Li Njisurufu O phosphate Nina Application Benefits um 1 · 13 g (2.1 X 10 one ^{3 niol)} 24 hours a large excess of PCI ₅ 8.75 g of the (0.042ηιο I) at a temperature of 160 ^e C heating did.

 (2) After standing to cool, distilled water was gently added while cooling the container with ice, and the insoluble matter was collected on a G-4 glass filter.

 (3) The residue was washed twice in distilled water, collected on a glass filter and dried.

Yield 1.07g in this good earthenware pots (2 x 10- ³ raol), was synthesized yield 95¾ Device Seo off Henin preparative port Li Njisurufu O Niruku Rorai de.

 The reaction formula for this synthesis process is shown in Fig. 5A. Reference numeral 100 indicates a synthesized phosphinyl chloride synthesized by bathophenant.

 1-2. Synthesis of salicylamine

 (1) 2.3g of sodium (0.1no dissolved in 15ml of anhydrous methanol), 40nl of anhydrous dimethylsulfoxide and 6.3nl (0.044iaol) of o-methoxybenzylamine are added and stirred for 24 hours. Returned.

 ②After that, distilled water is added while distilling off the solvent and cooling the vessel.

(3) After further concentrating to approximately 50ίΒ I, it was washed with benzene.

を Adjust the eyebrows to PH9 with 2.4N hydrochloric acid, collect the precipitate, and dry it. After drying, it was recrystallized with ethanol.

The Yo U in to yield 2.779 (2.25 ^10-2 11101), was synthesized Sarichirua Mi emissions at yield 5.

 The reaction formula for this synthesis process is shown in FIG. 5B. Symbol 200 indicates synthesized salicylamine

 1-3. Synthesis of bis (o-hydroxybenzylamino-sulfonyl) phosphine

① distilled water 20nN to Na0H 3 g (0.075rao l) and Sari Chirua Mi emissions 0 obtained above 1-2. 7 g (5.6 X 10- 3 Π) θ I) was dissolved _β

② above 1 in the aqueous solution - dimethyl Chi Ruhorumua Mi de solution 10 m l of the resulting Baso Fenan collected by filtration Li Njisurufu O Niruku port Lai de 0.5g (9.4x 10- ⁴ mo l) was added dropwise in 1.

 (3) The mixture was stirred at room temperature (20 to 25) for 2 hours. The precipitate was collected on paper, washed with distilled water, and dried.

The good cormorants in to yield ^{0.36g (5.1 x 10- 4 rao l} ), bis 55% yield - was synthesized (o human de Loki Shibenjirua Mi Nosurufu O sulfonyl) Bruno Seo off Henin preparative port Li down.

 The reaction formula for this synthesis process is shown in FIG. 5C. The bis (o-hydroxybenzylaminosulfonyl) synthesized with the symbol 300 indicates a soft-enantine ring.

 1-4. Synthesis of tris (bis (o-hydroxybenzylamino-sulfonyl) phenol) and iron (D)

① the 1 -3 resulting bis (o - hydroxycarboxylic benzyl A Mi Nosurufu O sulfonyl) Bruno Seo off Wenan collected by filtration Li down 2 g (2.85 x 10- ⁴ nol) and the _{FeCI 2 '4H 2 0 18.86g (} 9.5 x 10- 5 no I) and NaCI0 ₄ 0.5g were dissolved in dimethylformamide A mi de 10 nl.

 ② Stir at room temperature (20-25C) for 1 hour

 (3) After that, a large amount of water was injected, and the precipitate was collected on paper.

洗浄 After washing with distilled water,

The good cormorants in to yield 0.19 g (8.5 X 10 one ⁵ mol), Application Benefits scan in a yield 89¾ (bis (o - hydroxycarboxylic benzyl A mini Nosurufu O two Le) Baso off Enan preparative port Li down) Iron (I) was synthesized.

 The reaction formula for this synthesis process is shown in Fig. 5D.

Growth of tris (bis (o-hydroxybenzylaminosulfonyl) bathophenantine) iron (E)

 (1) Tris (bis (o-t-doxybenzylamino-sulfonyl) -no, 'so-foenant-mouth-lin) obtained from I Iron (H) 1 X 10-3 IBO I / I and NaCIO * The electrolyte was prepared by dissolving 0.1 IBO I / I in anhydrous methanol.

② Using this electrolyte, the working electrode is ITO, the counter electrode is platinum of the same area, the reference electrode is SCE, and the constant current of 5 // A / CII ^{2 to} 0.1 BA / CII ² is the ITO electrode. The anode was subjected to force source electrolysis so as to become an anode, and a red film was deposited on the anode. In this experiment, a constant current with a current density of 50 // A / en ² was briefly energized for 9 minutes.

 (3) After that, the ITO electrode was washed with anhydrous methanol and air-dried.

I. Tris (bis (o-hydroxybenzylaminosulf) Nil) エ エ エ リ 鉄 鉄 口 ク 口 口 口 ク 口

The good cormorants To iron complex鼋解polymerization obtained on the anode layer in the measurement of cyclic clicking voltaic Nme preparative Lee in aC I0 ₄ § Se Bok two Bok in drills 0. 1 mo I / I Fig. 7, which changed from red to pale yellow at the oxidation potential of +1.2 V vs. SCE and returned from pale yellow to red at the reduction potential of +1.0 V vs. SCE, is the cyclic voltammetry in this example. And FIG. 8 shows the electronic spectrum in this example. Here, measurement conditions of re-Gu Li tree Kuborutanme preparative rie of f Ig.7 the scanning speed: 5 0 nV / sec, an electrolyte solution: 0.1 »ol / £ N a C £ 0 4 § Se Toni DOO drill, Counter electrode: Platinum, Reference electrode: SCE. The measurement conditions of the electron scan Bae-vector of Fig.8 is the electrolyte:. 0 l raol / £ N a C £ 0 4 water, counter electrode: platinum, reference electrode: a SCE.

W. Manufacture of electoric chromic display elements

 Based on the above facts, an electrochromic display device as shown in Fig. 6 was manufactured.

 That is, a transparent electrode 2 made of ITO is formed on a glass substrate which is a substrate 1 of the display electrode, and the electrode (2) is used as an anode to perform a process of forming a tris (bis (ot) Display electrode 4 made of doxybenzylaminosulfonyl) nosofenantolerin) iron (Π) was prepared as a polymer film and used as display 脷.

On the other hand, a transparent electrode 7 made of an ITO film is also formed on the glass substrate, which is the substrate 8 on the opposite electrode side, and an oxidation-reduction substance As a counter electrode, a counter electrode 9 was formed using Prussian blue with a stable reduction reaction, and used as a counter electrode.

The display and圃and the counter electrode, through a white background plate 6 is opposed Ri by the sheet Lumpur material 1 0, NaCI0 ₄ and to 0.1 no 1/1 electrolyte 5 within the enclosed space An acetonitrile solution was enclosed to make an electronic display device.

The drive voltage of this display element was IV, and the repetitive operation was extremely stable. The response speed was 0.5 seconds, the lifetime is 1 X 1 0 ⁴ or more times.

 (Industrial applicability)

 The phenanthroline phosphorus derivative and the viviridine derivative of the present invention can be obtained by an electrolytic deposition method or an electrolytic polymerization method without using a carrier such as a polymer using a metal complex having these derivatives as a ligand. It can be easily fixed on the electrode. Therefore, when the metal complex formed in this manner is used as an EC material in an electronic-port chromic display device, an indispensable polymer or a colored conductive polymer is required. The film can be formed directly on the electrode by the electrolytic deposition method without using any electrode, so that the response speed is faster than that of the solution type, and there is no problem such as color unevenness. Thus, a clear display can be made.

Claims

 (1)

 9 10 1 2 At least one of the following functional groups R is substituted in at least one of the positions 3 to 8;  R: -C00H, -R'-COOH (Where R 'is CH ₂ n  -(-C H 2 n -S—,-S-C H 2-^-S  n  — ^ J—.-S 03-,-S O 2-, One C O N H—, one C O O—, one C O—, SO 2 N H + C H2 + _n ,

- SO 2 N H- CH 2 ten _n,  — (O—SO 2 N H, —SO 2 N H or 1 O—, and n is any natural number.) (2) A metal complex having a ligand of the phenanthine-opened derivative according to claim 1 as a ligand is polymerized by an electrolytic deposition method to form a film on a transparent electrode, which is used as a display electrode or a counter electrode. An electrochromic display element characterized in that it is used as an electrochromic display element. (3)

 9 10 1 2  At least one of the following functional groups R is substituted in at least one of the positions 3 to 8;

 (Where R 'is "CH2H" n, -f CK 2 ^-S-. one S + CH 2+ _n S one, L ^ —-so ₃ -,-so 2-, One C O N H—, One C O O—, One C O—

n, One so 2 N H- c H 2 + _n ,  O} —SO 2 NH, —SO 2 NH or 1 O—, and n is an arbitrary natural number. ) (4) The phenanthine-containing phosphorus derivative according to claim 3 is a ligand An electrochromic display element characterized in that a metal complex is polymerized by an electrolytic polymerization method to form a film on a transparent electrode, and this is used as a display electrode or a counter electrode.  (5) 2, 2 *-Bibiridyl 4 3 3 '4'

At least one of the following functional groups R is substituted at at least one of the 3 to 5 or 3 ′ to 5 ′ positions of  R: -COOH.-R'-COOH, (where R, is + CH 2 + _n ,-CH 2 ^ lf S—, SC H2 ten _{n, - S -, - θ} ^^  -S O 3 I,-S O 2 I, I C O N H—, It is one C O O—, one C O—, or —O—, and n is any natural number. ) (6) A metal complex having the biviridyl derivative according to claim 5 as a ligand is polymerized by an electrolytic deposition method to form a transparent electrode, which is used as a display electrode or a counter electrode. An electronic aperture display element characterized by an octopus.

A viviridyl derivative characterized by substituting at least one of the 3 to 5 or 3 ′ to 5 ′ positions of any one of the following functional groups R:

 (Where R 'is + C H2 n, One, — S + C H2 + _n , — S-, S 0 ₃ -,-S 0 _2- ,

 One C O N H—, _ C O O—, one C O—, or  One 0—, and n is an arbitrary natural number. ) (8) A metal complex coordinated with the biviridyl derivative according to claim 7 is polymerized by an electrolytic polymerization method to form a film on a transparent electrode, and this is used as a display electrode or a counter electrode. Characterized by and Electronic display device.  (9) Methyl 1, 10 — phenolic port The phenolic port according to claim 1, which has a peroxy acid group obtained by the reaction of phosphorus with metal sodium and carbon dioxide. Lin derivatives.  4. The fluorinated compound according to claim 3, which has an aniline group obtained by reacting (10) 1,10-phenylene-containing carboxylic acid chloride with o-phenylenediamine. Enanthate lin derivatives. (11) Obtained by the reaction of nosofenanthine-containing rinsulfonyl chloride with a primary amine having a phenoxy group —> — Claim 3 with S 02 H N C

_Linoleic derivative of  8. The biviridyl derivative according to claim 7, which has an aniline group obtained by reacting (12) 2,2'-biviridylcarboxylic acid chloride with o-phenylenediamine.  (13) The compound according to claim 3 or 7 is reacted with a metal salt to form a metal complex, and the metal complex is subjected to electric field polymerization to form a polymer on the electrode to be used as a display electrode. Manufacturing method of electronic microdisplay device  (14) An electronic device characterized in that the compound according to claim 1 or 5 is polymerized by an electrolytic deposition method to form a film on a transparent electrode, and this is used as a display electrode or a counter electrode. Manufacturing method of rochroic display element