WO2008077864A1 - Colorant électrochrome commutable cathodique, sa formule électrochrome et procédé de fabrication d'une cellule électrochrome - Google Patents

Colorant électrochrome commutable cathodique, sa formule électrochrome et procédé de fabrication d'une cellule électrochrome Download PDF

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Publication number
WO2008077864A1
WO2008077864A1 PCT/EP2007/064229 EP2007064229W WO2008077864A1 WO 2008077864 A1 WO2008077864 A1 WO 2008077864A1 EP 2007064229 W EP2007064229 W EP 2007064229W WO 2008077864 A1 WO2008077864 A1 WO 2008077864A1
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WO
WIPO (PCT)
Prior art keywords
electrochromic
substituted
hydroxy groups
partially unsaturated
saturated
Prior art date
Application number
PCT/EP2007/064229
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German (de)
English (en)
Inventor
Andreas Kanitz
Wolfgang Roth
Markus True
Original Assignee
Siemens Aktiengesellschaft
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Publication of WO2008077864A1 publication Critical patent/WO2008077864A1/fr

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Classifications

    • 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
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms

Definitions

  • Electrochromic formulation thereof and process for making an electrochromic cell
  • the invention relates to a cathodic electrochromic dye, an electrochromic formulation thereof and a process for producing an electrochromic cell.
  • the cells are used in particular for the production of displays.
  • Electrochromic displays based on organic materials normally consist of a layer of special composition, which in the case of a display is located between electrodes arranged perpendicular to one another.
  • electrochromic formulations whose dye is a pH indicator and there are electrochromic formulations whose essential ingredient is a redox-active dye.
  • the latter are known, for example, from DE 10 2005 032 316.2.
  • the dye is usually in a dispersed in a solvent white pigment matrix.
  • a typical solvent is z.
  • B. diethylene glycol, the white pigment is z. For example, titanium dioxide.
  • a disadvantage of the known systems is their short life.
  • the degradation of the transparent electrode can take place, for example, as a consequence of the proton activity.
  • the electrochromic systems based on pure redox materials as in the so-called viologen-based systems, a color contrast deterioration occurs because of the pimerization of the reduced species (formation of aromatic stacks by the ⁇ -electron planes), which leads to a color shift of blue to purple (hence also called viologen) and leads to poor solubility.
  • the pimient species can no longer be oxidized completely electrically (converted to the colorless state), so that the contrast between switched tem, so under tension and de-energized state is always lower.
  • metallocenes and metallocene derivatives are used to increase the long-term stability of electrochromically active formulations based on pure redox materials with cathodic electrochromic.
  • This class of compounds has been found to be suitable because it protects the electrodes, in particular the anode, i.
  • the electrochromium at the cathode transitions to a reduced colored state, the anode is protected from electrochemical corrosion by instead oxidizing the metallocene at the anode without causing a significant change in color in the short term.
  • the object of the present invention is to provide formulations for further electrochromic systems which have improved long-term stability.
  • the subject of the present invention is therefore a cathodically switchable dye KE or KE '.
  • R is an alkyl moiety Ci-C 2O , unbranched saturated or branched saturated and partially unsaturated and / or substituted by hydroxy groups or aryl moiety substituted by alkyl and / or hydroxy groups, or the substituents R are bifunctional alkylene groups Ci- C20, unbranched saturated or branched saturated such as partially unsaturated or and / or substituted by hydroxy groups, so that they form in the alkylation step polymers KE or KE '.
  • the invention provides an electrochromically active formulation having at least one cathodically switchable electrochromic formula of the formula KE or KE '(oxidizing agent) which contains at least one anodically reacting stabilizing material as a pendant,
  • R is an alkyl moiety of C1-C20, straight-chain saturated or branched saturated and partially unsaturated and / or substituted by hydroxyl groups or aryl moiety is substituted by alkyl and / or hydroxy groups, or the substituents R are bifunctional alkylene moieties Ci- C 2O, unbranched saturated or branched saturated as well as partially unsaturated or and / or substituted by hydroxy groups, so that they form in the alkylation step polymers KE or KE '.
  • the subject of the invention is a process for producing an electrochromic cell by introducing a layer of an electrochromic formulation with at least one cathodically switchable dye KE or KE 'of the general formula:
  • R is an alkyl moiety of C1-C20, straight-chain saturated or branched saturated and partially unsaturated and / or substituted by hydroxyl groups or aryl moiety is substituted by alkyl and / or hydroxy groups, or the substituents R are bifunctional alkylene moieties Ci- C 2O, unbranched saturated or branched saturated as well as partially unsaturated or and / or substituted by hydroxy groups, so that they form polymers KE or KE 'in the alkylation step.
  • Cathodically switchable electrochromic dye means that the desired dye formation (dye representation) is formed at the cathode.
  • the cathodically switchable dyes according to the invention achieve long lifetimes when they are molar mixed in a formulation together with an anodically switchable counterpart, that is to say an anodically reacting stabilizing material.
  • an anodically switchable counterpart that is to say an anodically reacting stabilizing material.
  • This may be both a metallocene derivative and the class of materials known from 2006E24127.
  • the cathodic electrochromic materials KE are particularly attractive in that, owing to their low reduction potentials, they can be coated even ⁇ 1V, independently of the anodically switching material.
  • electrochromic formulations which can be produced from these materials form stable layers even on large surfaces in an electrochromic component which can be produced therefrom, which makes the application of e.g. allowed by "roll-to-roll” processes.
  • 2,5-Di (pyridin-4-yl) pyrimidine KE4 from compound 3 (0.75 g, 3.2 mmol, 1 equiv) and 1-bromo-decanol (4.1 g, 16.0 mmol, 5 Aquiv.). Boil in 10 ml of acetonitrile and 10 ml of nitrobenzene on the RF for at least 6 h. Recrystallization from ethanol / ethyl acetate.
  • the resulting, very fine precipitate can be filtered off with suction through a fine-pored glass frit and washed with toluene.
  • the residue is again boiled in toluene, filtered off with suction and washed with ether.
  • An additional recrystallization is possible from ethanol / ethyl acetate.
  • the resulting, yellowish precipitate can be filtered off with suction through a fine-pored glass frit and washed with acetonitrile and ether.
  • An additional recrystallization is possible from ethanol / ethyl acetate.
  • the synthesis takes place in a glove box under an inert gas atmosphere.
  • the filtrate is concentrated by rotary evaporation, the oily residue is dissolved in methylene chloride and shaken out in a separating funnel with water. The orange-brown organic phase is separated off and concentrated on a rotary evaporator to dryness. The remaining residue is dissolved in a little THF and treated with methanol. The resulting precipitate is filtered off, washed with methanol and dried in vacuo at RT.
  • slurry 2_ (10 g, 30.7 mmol, 1 equiv.) Along with phenacyl chloride (5.3 g, 34 mmol, 1.1 equiv.) In 100 mL acetonitrile and heat to reflux. First, a clear, yellowish solution is formed, from which a yellowish precipitate precipitates after a few minutes.
  • reaction is complete after about 2 h. If no starting material can be detected by thin-layer chromatography, the suspension is allowed to cool to RT. The resulting white precipitate is filtered off with suction, once each with acetonitrile, acetone nitrile / ether and pure ether and dried in vacuo at RT.
  • the synthesis takes place in a glove box under an inert gas atmosphere.
  • cathodic electrochromic e.g., KEl
  • anodic material e.g., ferrocene, AM or AM '
  • titanium dioxide e.g., ferrocene, AM or AM '
  • diethylene glycol e.g., ethylene glycol
  • cathodic electrochromes can be connected with a lifetime of at least 10 6 switching cycles, cl) In this way, for example, di- (heptyl) -substituted quaternary salt of 2,5-di (pyridin-4-yl) pyrimidine KEl as a cathodic electrochromic switched to green.
  • the invention relates to a cathodic electrochromic dye, an electrochromic formulation thereof and a process for producing an electrochromic cell.
  • the cells are used in particular for the production of displays.
  • the formulation is characterized in particular by the fact that the cathodically switchable dye has a low oxidation potential.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention concerne un colorant électrochrome cathodique, sa formule électrochrome et un procédé de fabrication d'une cellule électrochrome. Ces cellules servent en particulier à la fabrication d'écrans. La formule se caractérise en particulier en ce que le colorant commutable cathodique présente un faible potentiel d'oxydation.
PCT/EP2007/064229 2006-12-21 2007-12-19 Colorant électrochrome commutable cathodique, sa formule électrochrome et procédé de fabrication d'une cellule électrochrome WO2008077864A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610061999 DE102006061999A1 (de) 2006-12-21 2006-12-21 Kathodisch schaltbarer elektrochromer Farbstoff elektrochrome Formulierung daraus und Verfahren zur Herstellung einer elektrochromen Zelle
DE102006061999.4 2006-12-21

Publications (1)

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WO2008077864A1 true WO2008077864A1 (fr) 2008-07-03

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DE (1) DE102006061999A1 (fr)
WO (1) WO2008077864A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013193991A (ja) * 2012-03-21 2013-09-30 Ricoh Co Ltd エレクトロクロミック化合物、エレクトロクロミック組成物及び表示素子
WO2014208775A1 (fr) 2013-06-27 2014-12-31 Ricoh Company, Ltd. Composé électrochromique, composition électrochromique, élément d'affichage et élément de gradation
JP2015027987A (ja) * 2013-06-27 2015-02-12 株式会社リコー エレクトロクロミック化合物、エレクトロクロミック組成物及び表示素子及び調光素子
KR20170128453A (ko) * 2015-03-13 2017-11-22 가부시키가이샤 리코 일렉트로크로믹 화합물, 일렉트로크로믹 조성물, 일렉트로크로믹 소자, 및 일렉트로크로믹 조광 소자

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008024259A1 (de) * 2008-05-20 2009-12-31 Siemens Aktiengesellschaft Elektrochrome Formulierung und Verfahren zur Herstellung einer elektrochromen Formulierung; Verwendung der Formulierung und organisches elektronisches elektrochromes Bauteil
DE102009023309A1 (de) 2009-05-29 2010-12-16 Siemens Aktiengesellschaft Elektrochrome Formulierung, Herstellungsverfahren dazu und elektrochromes organisches Bauelement
WO2016147543A1 (fr) * 2015-03-13 2016-09-22 Ricoh Company, Ltd. Composé électrochromique, composition électrochromique, élément électrochromique et élément d'obscurcissement électrochromique

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JPS6099189A (ja) * 1983-11-04 1985-06-03 Ricoh Co Ltd エレクトロクロミツク表示素子
US5507974A (en) * 1992-12-11 1996-04-16 Hoechst Aktiengesellschaft Aromatic, substituted pyrimidine compounds, methods for the preparation thereof, and use thereof
US20010030794A1 (en) * 2000-01-13 2001-10-18 Horst Berneth Electrochromic device
US20030234379A1 (en) * 2002-06-20 2003-12-25 Burrell Anthony K. Electrochromic salts, solutions, and devices

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DE4423098A1 (de) * 1994-07-01 1996-01-04 Hoechst Ag Verwendung von Pyrimidingruppen enthaltenden konjugierten Verbindungen als Elektrolumineszenzmaterialien

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JPS6099189A (ja) * 1983-11-04 1985-06-03 Ricoh Co Ltd エレクトロクロミツク表示素子
US5507974A (en) * 1992-12-11 1996-04-16 Hoechst Aktiengesellschaft Aromatic, substituted pyrimidine compounds, methods for the preparation thereof, and use thereof
US20010030794A1 (en) * 2000-01-13 2001-10-18 Horst Berneth Electrochromic device
US20030234379A1 (en) * 2002-06-20 2003-12-25 Burrell Anthony K. Electrochromic salts, solutions, and devices

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TAKAHASHI KAZUKO ET AL: "Synthesis and characterization of new conjugation-extended viologens involving a central aromatic linking group", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, CHEMICAL SOCIETY. LETCHWORTH, GB, 1992, pages 620 - 622, XP008089309, ISSN: 0022-4936 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013193991A (ja) * 2012-03-21 2013-09-30 Ricoh Co Ltd エレクトロクロミック化合物、エレクトロクロミック組成物及び表示素子
WO2014208775A1 (fr) 2013-06-27 2014-12-31 Ricoh Company, Ltd. Composé électrochromique, composition électrochromique, élément d'affichage et élément de gradation
JP2015027987A (ja) * 2013-06-27 2015-02-12 株式会社リコー エレクトロクロミック化合物、エレクトロクロミック組成物及び表示素子及び調光素子
EP3013840A4 (fr) * 2013-06-27 2016-07-13 Ricoh Co Ltd Composé électrochromique, composition électrochromique, élément d'affichage et élément de gradation
US9688706B2 (en) 2013-06-27 2017-06-27 Ricoh Company, Ltd. Electrochromic compound, electrochromic composition, display element, and dimming element
CN105339376B (zh) * 2013-06-27 2017-08-08 株式会社理光 电致变色化合物、电致变色组合物、显示元件和调光元件
KR20170128453A (ko) * 2015-03-13 2017-11-22 가부시키가이샤 리코 일렉트로크로믹 화합물, 일렉트로크로믹 조성물, 일렉트로크로믹 소자, 및 일렉트로크로믹 조광 소자
KR102027049B1 (ko) * 2015-03-13 2019-09-30 가부시키가이샤 리코 일렉트로크로믹 화합물, 일렉트로크로믹 조성물, 일렉트로크로믹 소자, 및 일렉트로크로믹 조광 소자
US10988684B2 (en) 2015-03-13 2021-04-27 Ricoh Company, Ltd. Electrochromic compound, electrochromic composition, electrochromic element, and electrochromic dimming element

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DE102006061999A1 (de) 2008-06-26

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