WO1991002723A1 - Derive de phenanthroline, derive de bipyridile et element d'affichage electrochrome - Google Patents

Derive de phenanthroline, derive de bipyridile et element d'affichage electrochrome Download PDF

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Publication number
WO1991002723A1
WO1991002723A1 PCT/JP1990/001070 JP9001070W WO9102723A1 WO 1991002723 A1 WO1991002723 A1 WO 1991002723A1 JP 9001070 W JP9001070 W JP 9001070W WO 9102723 A1 WO9102723 A1 WO 9102723A1
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Prior art keywords
electrode
derivative
display
metal complex
display element
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PCT/JP1990/001070
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English (en)
Japanese (ja)
Inventor
Hirofusa Shirai
Toshiki Koyama
Takahisa Fukuzawa
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Kabushiki Kaisha Sankyo Seiki Seisakusho
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Priority claimed from JP1215019A external-priority patent/JPH0381264A/ja
Priority claimed from JP2136100A external-priority patent/JP2502399B2/ja
Application filed by Kabushiki Kaisha Sankyo Seiki Seisakusho filed Critical Kabushiki Kaisha Sankyo Seiki Seisakusho
Publication of WO1991002723A1 publication Critical patent/WO1991002723A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials

Definitions

  • Phosphorus derivatives Phosphorus derivatives, biviridyl derivatives, and electrochromic display elements
  • 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.
  • Electro-chromic display devices 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention provides a phosphorene derivative having a 1,10-phenylene derivative.
  • At least one of the positions 3 to 8 is substituted with one of the following functional groups R.
  • n is an arbitrary natural number.
  • 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.
  • 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.
  • 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.
  • the biliyl derivative of the present invention is a 2,2′-biviridyl compound.
  • 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
  • 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.
  • 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:
  • 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.
  • electrolytic deposition or electrolytic polymerization can be performed on the phenolic skeleton and the viviridine skeleton.
  • 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
  • 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.
  • 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.
  • 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.
  • the functional group R is, specifically,
  • 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.
  • 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.
  • 1, 10 — phenanthine phosphorous-3-carboxylic acid is It is obtained by the oxidation of 1,10-phenylen-3-methyl.
  • 1,10-phenylene-l-butyric acid is obtained by oxidation of 1,10-phenylene-l-l-methyl.
  • 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.
  • 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
  • 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.
  • derivatives having different substitution positions of one C H2 C 0 OH group can be obtained by the same dilation.
  • 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.
  • 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.
  • the functional group R is, specifically,
  • 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.
  • 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
  • the viviridyl derivative according to the third aspect of the present invention is also 2, 2'-viviridyl.
  • 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.
  • 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.
  • —4-carboxy-2,2 ⁇ —biviridyl having one C 00 H group is a methyl group of 4,4-dimethyl-2,2′-biviridine.
  • 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.
  • the biviridyl derivative according to the fourth aspect of the present invention is also a 2,2′-biviridyl derivative.
  • 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.
  • 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.
  • the phosphorus derivative and the biviridyl derivative are represented by the following formulas (m) and (IV), respectively.
  • M is a transition metal
  • X is a counter anion
  • phen is 1,10-phenanine-containing phosphorus
  • bpy is 2,2′-biviridyl
  • R is Enables such electrolytic deposition
  • n shows a number of functional groups
  • m is a variable ranging from 0 to 6, respectively [Phi)
  • the transition metal serving as the central element is not particularly limited, and various ones can be applied.
  • 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.
  • 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.
  • 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 ( ⁇ ) complex.
  • This shows the reaction process.
  • 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!
  • C jg O 4 C jg O 4
  • DMF N, N'-dimethylformamide
  • N-formamide formamide
  • DMS 0 dimethyl sulfoxide
  • THF Tetrahydrofuran
  • acrylonitrile 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 ⁇ 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.
  • the electrolyte used for this growth is, for example, Alkali metal salts such as KC j ?, alkali metal perchlorates such as LiC ⁇ 4, and perchlorines such as tetraethylammonium perchlorate (hereinafter referred to as ⁇ ⁇ ⁇ )
  • Alkali metal salts such as KC j ?
  • alkali metal perchlorates such as LiC ⁇ 4
  • perchlorines such as tetraethylammonium perchlorate (hereinafter referred to as ⁇ ⁇ ⁇ )
  • ⁇ ⁇ ⁇ 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.
  • a substituent having a C 0 O ⁇ (Q ⁇ —OH group is present at the terminal of 1,10-phenanthroline or 2,2'-biviridyl
  • 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 £,
  • Fig. 5A-Fig. 5D shows that the functional group R
  • the electrolytic deposition can be similarly performed, for example, having an “ ⁇ ⁇ group at a terminal.
  • the group is dissolved in an electrolytic solution and reduced or oxidized on an electrode to form the group.
  • Metal complex having a ligand of a benzoyl derivative or a viviridyl derivative also dissolves in the electrolyte and oxidizes on the electrode.
  • 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.
  • the ij group 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.
  • 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.
  • 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.
  • 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.
  • FIG. 6 is a drawing showing a schematic structure of an embodiment of the electronic mouthpiece display device of the present invention.
  • 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
  • 8 is a facing electrode.
  • An electrode substrate, 9 is a counter electrode member
  • 10 is a sealing material.
  • 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 ( ⁇ ) 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.
  • a known conductive film material for example, tin oxide (SnO 2), indium oxide (In 203) (IT 0>), etc.
  • An insulating material such as an epoxy-based insulating material is employed.
  • 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 ⁇ 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
  • (Z r (0 H) 4 ⁇ ⁇ ⁇ 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.
  • 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.
  • a metal complex having a ligand of the phenantine-containing derivative and the bipyridyl derivative according to the present invention for example, cobalt phthalocyanine (CoPc) @prussian blue (PB), which is stable in a reduction reaction, can be used.
  • CoPc cobalt phthalocyanine
  • PB prussian blue
  • 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.
  • 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
  • phen represents a phenanthroline
  • Ac represents one CH2COOH
  • 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.
  • reaction solution was adjusted to about PH 4 with 1 N—H C &, and the precipitate was collected by filtration and dried.
  • 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.
  • acetonitrile containing 0.5 M Ca (C £ O 4) 2 was used as the electrolyte.
  • reaction solution was naturally filtered to remove the generated ⁇ 2. Further, ⁇ 2 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.
  • the precipitate was dissolved in a small amount of dimethylformamide (DMF), and FeCi2.4H20 (bQag) was added.
  • DMF dimethylformamide
  • bQag FeCi2.4H20
  • the yield of the obtained fin bodies was 68 mg.
  • 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.
  • reaction solution was naturally filtered to remove the generated ⁇ 2. Furthermore, ⁇ 2 on the paper was extracted by washing with ripened water.
  • DDMF was distilled off as much as possible without ripening.
  • 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.
  • 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.
  • Bis (o-hydroxybenzylamino-sulfonyl) bis (enoxy) sulfonate is synthesized from sodium naphthyl sodium phosphate and sulfonate.
  • Reference numeral 100 indicates a synthesized phosphinyl chloride synthesized by bathophenant.
  • 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.
  • Tris bis (o-t-doxybenzylamino-sulfonyl) -no, 'so-foenant-mouth-lin
  • the electrolyte was prepared by dissolving 0.1 IBO I / I in anhydrous methanol.
  • the working electrode is ITO
  • the counter electrode is platinum of the same area
  • the reference electrode is SCE
  • 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.
  • a constant current with a current density of 50 // A / en 2 was briefly energized for 9 minutes.
  • 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.
  • 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 ( ⁇ ) was prepared as a polymer film and used as display ⁇ .
  • 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 ⁇ 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.
  • 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.

Abstract

Dérivés de phénanthroline et de bipyridyle dont chacun possède un substituant qui est susceptible de subir une déposition électrolytique ou une polymérisation électrolytique afin d'être produit directement sous forme de film. Ces dérivés peuvent être utilisés lors de la fabrication d'éléments d'affichage électrochromes ou analogue.
PCT/JP1990/001070 1989-08-23 1990-08-22 Derive de phenanthroline, derive de bipyridile et element d'affichage electrochrome WO1991002723A1 (fr)

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JP1215019A JPH0381264A (ja) 1989-08-23 1989-08-23 フェナントロリン誘導体、ビピリジル誘導体およびエレクトロクロミック表示素子
JP1/215019 1989-08-23
JP2/136100 1990-05-25
JP2136100A JP2502399B2 (ja) 1990-05-25 1990-05-25 エレクトロクロミック表示素子およびその製造方法

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WO1991002723A1 true WO1991002723A1 (fr) 1991-03-07

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WO1994024123A1 (fr) * 1993-04-21 1994-10-27 Kodak Limited Complexes de bipyridines sensibles aux ions

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JPS63180950A (ja) * 1987-01-22 1988-07-26 Konica Corp 熱カブリの改良された熱現像感光要素
JPS63502452A (ja) * 1986-01-23 1988-09-14 ディビッドソン，ロバ−ト・スチ−ブン 時間分解発光結合イムノアッセイ、それに使用する金属標識された結合パートナー、および該パートナーの製造方法

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JPS5730728A (en) * 1980-08-01 1982-02-19 Hitachi Ltd Linear high polymer
US4611890A (en) * 1984-01-24 1986-09-16 Research Corporation Redox chromophore compounds and electrodes of metal containing substituted bipyridines
CN85107032A (zh) * 1985-09-20 1987-04-01 弗·哈夫曼-拉罗切有限公司 钌络合物的制备和应用
JPS63502452A (ja) * 1986-01-23 1988-09-14 ディビッドソン，ロバ−ト・スチ−ブン 時間分解発光結合イムノアッセイ、それに使用する金属標識された結合パートナー、および該パートナーの製造方法
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CHEMICAL ABSTRACTS, Vol. 110, No. 10, 87480t, (06.03.89), P. 845, FRANCIS MUELLER et al., (F. Hoffman-La Roche und C.A. - G.); & CN,A,85 107 032, (01.04.87), (Family: none). *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994024123A1 (fr) * 1993-04-21 1994-10-27 Kodak Limited Complexes de bipyridines sensibles aux ions

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