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  • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
  • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
  • H10K2102/10—Transparent electrodes, e.g. using graphene
  • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
  • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO

Definitions

• the present invention relates to a spiro-type organic material and an organic electroluminescent device using the same, and more particularly, a spiro-type organic material which can obtain a short wavelength light emission that can be used for an organic electroluminescent device, which is a kind of display, with high efficiency. And it relates to an organic electroluminescent device using the same.
• Organic semiconductors are being developed for numerous types of electronic equipment applications.
• the organic electroluminescent device is simpler in structure than other flat panel display devices such as liquid crystal display (LCD), plasma display panel (PDP) and field emission display (FED), has various advantages in manufacturing process, and has high luminance and viewing angle. Due to its excellent characteristics, fast response speed and low driving voltage, development is being actively conducted to be used as a light source for a flat panel display such as a wall-mounted TV or a back light of a display, an illumination, a billboard.
• LCD liquid crystal display
• PDP plasma display panel
• FED field emission display Due to its excellent characteristics, fast response speed and low driving voltage, development is being actively conducted to be used as a light source for a flat panel display such as a wall-mounted TV or a back light of a display, an illumination, a billboard.
• an organic electroluminescent device recombines holes injected from an anode and electrons injected from a cathode when a DC voltage is applied to form an exciton, an electron-hole pair, and is converted into light by transferring energy of the excitons to a light emitting material.
• spiro-type compounds are known to have excellent thermal stability and device properties.
• a material having a blue light emitting layer in a short wavelength region using a spiro form of the compound there is no report on a material having a blue light emitting layer in a short wavelength region using a spiro form of the compound.
• the present inventors completed the present invention by finding that a compound having an asymmetric spiro form could solve the above problems while studying an aromatic compound capable of obtaining light emission of short wavelength with high efficiency.
• the present invention is to provide a spiro-type organic material and an organic electroluminescent device using the same, which can obtain light emission of short wavelength with high efficiency.
• the present invention provides a compound represented by the following formula (1).
• R 1 is phenyl, said phenyl is unsubstituted or substituted with one or two substituents independently selected from the group consisting of halogen, C 1-4 haloalkyl, cyano, phenyl and trimethylsilyl,
• R 2 is phenyl or naphthyl, said phenyl is substituted with one or two substituents independently selected from the group consisting of halogen, C 1-4 haloalkyl, cyano and trimethylsilyl.
• the compound represented by the formula (1) has a structure of spiro [benzo [c] fluorene-7,9'-fluorene] (spiro [benzo [c] fluorene-7,9'-fluorene]), It is more robust and harder to crystallize than conventional spyrophoric compounds. In addition, it has an asymmetric structure, and the secondary amine derivative is substituted, it is characterized in that the blue light emission is possible.
• R 1 is phenyl and the phenyl is unsubstituted or substituted with one or two substituents independently selected from the group consisting of fluoro, trifluoromethyl, cyano, phenyl and trimethylsilyl do.
• the phenyl is substituted with any one substituent selected from the group consisting of fluoro, trifluoromethyl, cyano, phenyl and trimethylsilyl.
• the phenyl is substituted with two trifluoromethyls.
• R 2 is phenyl and the phenyl is substituted with any one or two substituents independently selected from the group consisting of fluoro, trifluoromethyl, cyano and trimethylsilyl.
• the phenyl is substituted with any substituent selected from the group consisting of fluoro, trifluoromethyl, cyano and trimethylsilyl.
• the phenyl is substituted with two trifluoromethyls.
• the present invention provides a method for producing a compound represented by the formula (1), as shown in Scheme 1-1.
• R 1 and R 2 are as defined above.
• Step 1 is a step of preparing a compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula 1-2 with the compound represented by Chemical Formula 1-3.
• Toluene may be used as the solvent, and the reaction is preferably performed in the presence of palladium acetate (II), tri-t-butylphosphine, sodium t-butoxide, and the like.
• the compound represented by Chemical Formula 1-2 may be prepared as, for example, the following Scheme 1-2, and in the present invention, the compound represented by Chemical Formula 1-2 in the following Preparation Example was used.
• the present invention provides an organic light emitting device comprising the compound represented by the formula (1).
• the present invention also provides an organic electroluminescent device in which an organic thin film layer composed of a single layer or a plurality of layers including at least one light emitting layer is sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer is represented by Chemical Formula 1
• An organic electroluminescent device comprising an organic light emitting device comprising a compound is provided.
• the present invention provides a compound represented by the following formula (2).
• R 1 is phenyl, said phenyl is unsubstituted or substituted with one or two substituents independently selected from the group consisting of halogen, C 1-4 haloalkyl, cyano, phenyl and trimethylsilyl,
• R 2 is phenyl or naphthyl, said phenyl is substituted with one or two substituents independently selected from the group consisting of halogen, C 1-4 haloalkyl, cyano and trimethylsilyl.
• the compound represented by the formula (2) has a structure of spiro [benzo [de] anthracene-7,9'-fluorene] (spiro [benzo [de] anthracene-7,9'-fluorene]), and As a spy, the structure of the compound is more robust and difficult to crystallize. In addition, it has an asymmetric structure, and the secondary amine derivative is substituted, it is characterized in that the blue light emission is possible.
• R 1 is phenyl and the phenyl is unsubstituted or substituted with one or two substituents independently selected from the group consisting of fluoro, trifluoromethyl, cyano, phenyl and trimethylsilyl do.
• the phenyl is substituted with any one substituent selected from the group consisting of fluoro, trifluoromethyl, cyano, phenyl and trimethylsilyl.
• the phenyl is substituted with two trifluoromethyls.
• R 2 is phenyl and the phenyl is substituted with any one or two substituents independently selected from the group consisting of fluoro, trifluoromethyl, cyano and trimethylsilyl.
• the phenyl is substituted with any substituent selected from the group consisting of fluoro, trifluoromethyl, cyano and trimethylsilyl.
• the phenyl is substituted with two trifluoromethyls.
• the present invention provides a method for producing a compound represented by the formula (2), for example, Reaction Scheme 2-1.
• R 1 and R 2 are as defined above.
• Step 1 is a step of preparing a compound represented by Chemical Formula 2 by reacting the compound represented by Chemical Formula 2-2 with the compound represented by Chemical Formula 2-3.
• Toluene may be used as the solvent, and the reaction is preferably performed in the presence of palladium acetate (II), BINAP (2,2'-bis (diphenylphosphino) -1,1'-binaphthyl), sodium t-butoxide and the like.
• the compound represented by Chemical Formula 2-2 may be prepared, for example, as in Scheme 2-2.
• the compound represented by Chemical Formula 2-2 is used in the following Preparation Example.
• the present invention also provides an organic light emitting device comprising the compound represented by the formula (2).
• the present invention is an organic electroluminescent device in which an organic thin film layer consisting of a single layer or a plurality of layers including at least one light emitting layer is sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer is represented by the formula (2)
• An organic electroluminescent device comprising an organic light emitting device comprising a compound is provided.
• the compound of the spiro structure and the organic electroluminescent device using the same according to the present invention can obtain a short wavelength of light emission with high efficiency, and can be applied to various organic electroluminescent devices such as flat panel displays such as wall-mounted TVs, lighting or back light of displays. Can be used.
• 4-aminobenzonitrile (15 g) was added to a 2 L three-necked round bottom flask and stirred for 30 minutes under an argon atmosphere. After stirring for 30 minutes, bromobenzene (18.1 g) was added, dissolved in toluene (1 L), tris (dibenzylideneacetone) dipalladium (0) (1.06g), and tri-t-butylphosphine (0.23 g). , Sodium-t-butoxide (24.4 g) was added thereto and stirred at reflux for 18 hours. Filtration in hot state, the solid on the filter was washed with hot toluene, dichloromethane and the filtrate was concentrated under reduced pressure.
• reaction solution was extracted with water and methylene chloride, dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent.
• Example 2 to 76 The compound of Example 2 to 76 was prepared in the same manner as in Example 1, using Intermediates 2-2 to 2-76 instead of Intermediate 2-1. Structures and NMR data of Examples 2 to 76, respectively, are shown in Tables 6 to 20 below.
• the ITO transparent electrode having a thin film thickness of 100 nm was 40 mm ⁇ 40 mm ⁇ 0.7 m in size, and the substrate was ultrasonically cleaned in a distilled shoe in which detergent was dissolved for 10 minutes, and washed twice in distilled water for 10 minutes.
• a layer of a compound represented by the following formula (B) capable of hole transport on the compound layer represented by the formula (A) was formed by vacuum deposition at 80 nm.
• Example 1 of the present invention was mixed and deposited at a concentration of 5% as a blue dopant together with the compound represented by the following Formula C as a light emitting host on the compound layer represented by Formula B to form a light emitting layer having a thickness of 20 nm.
• a compound represented by the following Formula D which serves to inject and transport electrons on the emission layer, was vacuum deposited to a thickness of 25 nm.
• LiF lithium fluoride
• 120 nm thick aluminum were sequentially deposited on the electron injection and transport layer to form a cathode.
• the organic electroluminescent device was manufactured by the same method as Experimental Example 1, except that the compound of Example 10 was used instead of the compound of Example 1, which is a light emitting dopant material.
• the organic electroluminescent device was manufactured by the same method as Experimental Example 1, except that the compound of Example 71 was used instead of the compound of Example 1, which is a light emitting dopant material.
• the organic electroluminescent device was manufactured by the same method as Experimental Example 1, but using a compound represented by the following Formula E instead of the compound of Example 1, which is a light emitting dopant material.
• 1,8-dibromonaphthalene 50 g
• 4-chlorophenylboronic acid 30.1 g
• toluene 500 mL
• potassium carbonate 132.9 g
• water 250 mL
• Tetrakis (triphenylphosphine) palladium (0) 2.22 g
• the reaction solution was cooled to room temperature and extracted twice with ethyl acetate.
• the organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent.
• the material produced by concentration was separated by column using hexane and washed with methanol to obtain 35 g of a white powder.
• intermediate 1-4 (33.5 g) was added to 335 mL of carbon tetrachloride, and the mixture was stirred until it was completely dissolved. After confirming that intermediate 1-4 was completely dissolved, bromine (13.4 mL) was added thereto, and the mixture was refluxed for 72 hours. After completion of the reaction, the mixture was filtered under reduced pressure at room temperature, washed with an aqueous sodium hydroxide solution, and the filtered solid was vacuum dried to obtain 40.1 g of Intermediate 1.
• Example 2 to 76 The compound of Example 2 to 76 was prepared in the same manner as in Example 1, using Intermediates 2-2 to 2-76 instead of Intermediate 2-1. Structures and NMR data of the prepared Examples 2 to 76 are shown in Tables 21 to 35, respectively.
• the ITO transparent electrode having a thin film thickness of 100 nm was 40 mm ⁇ 40 mm ⁇ 0.7 m in size, and the substrate was ultrasonically cleaned in a distilled shoe in which detergent was dissolved for 10 minutes, and washed twice in distilled water for 10 minutes.
• a layer of a compound represented by the following formula (B) capable of hole transport on the compound layer represented by the formula (A) was formed by vacuum deposition at 80 nm.
• Example 1 of the present invention was mixed and deposited at a concentration of 5% as a blue dopant together with the compound represented by the following Formula C as a light emitting host on the compound layer represented by Formula B to form a light emitting layer having a thickness of 20 nm.
• a compound represented by the following Formula D which serves to inject and transport electrons on the emission layer, was vacuum deposited to a thickness of 25 nm.
• LiF lithium fluoride
• 120 nm thick aluminum were sequentially deposited on the electron injection and transport layer to form a cathode.
• the organic electroluminescent device was manufactured by the same method as Experimental Example 1, except that the compound of Example 10 was used instead of the compound of Example 1, which is a light emitting dopant material.
• the organic electroluminescent device was manufactured by the same method as Experimental Example 1, except that the compound of Example 71 was used instead of the compound of Example 1, which is a light emitting dopant material.
• the organic electroluminescent device was manufactured by the same method as Experimental Example 1, but using a compound represented by the following Formula E instead of the compound of Example 1, which is a light emitting dopant material.

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• 2013
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