KR20110011578A - Indolocarbazole derivatives and organoelectroluminescent device using the same - Google Patents

Abstract

PURPOSE: An indolocarbazole derivative is provided to obtain an organic electroluminescence device with low driving voltage and excellent luminous efficiency. CONSTITUTION: An indolocarbazole derivative is represented by chemical formula 1, wherein ICbz1 and ICbz2 are respectively selected from structures represented by chemical formulae 2-6. In chemical formulae 2-6, R1 and R2 respectively substituted or unsubstituted C1-20 alkyl group, substituted or unsubstituted C6-30 aryl group; Ar1 and Ar2 are respectively substituted or unsubstituted heteroarylamino group, stituted or unsubstituted C6-30 aryl group, substituted or unsubstituted C3-30 heteroaryl group; m and n are an integer of 0-3; and the sum of n and m is an integer of 1, 2, 3.

Description

Indolocarbazole derivatives and organoelectroluminescent device using the same

The present invention relates to an indolocarbazole derivative and an organic electroluminescent device comprising the same, the organic electroluminescent device comprising an indolocarbazole derivative according to the present invention is low in driving voltage and excellent in luminous efficiency.

The organic light emitting device is gradually expanding its application field to the display and lighting field of various electronic products, but the efficiency and lifespan characteristics are restricting the expansion of the application field. There is a lot of research going on. In terms of materials, the host-dopant system is mainly adopted as a method for maximizing luminous efficiency, and the dopant as a luminescent material is phosphorescent material, and CBP (4, 4'-N, N'-dicarbazol bipheny) and substances in which various substituents are introduced into carbazole (Japanese Patent Application Laid-Open No. 2008-214244, Japanese Patent Application Laid-Open No. 2003-133075) are known, but further improvement is required in terms of efficiency and lifespan characteristics.

The first object of the present invention is to provide a novel indolocarbazole derivative having characteristics of low driving voltage and high luminous efficiency of an organic light emitting display device.

In addition, the second technical problem to be solved by the present invention is to provide an organic electroluminescent device having improved properties by employing the indolocarbazole derivative.

In order to achieve the first problem, the present invention provides an indolocarbazole derivative of the following [Formula 1].

[Formula 1]

In [Formula 1],

ICbz1 and ICbz2 are each independently selected from the structures represented by the following [Formula 2] to [Formula 6],

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6]

In this case, R1 and R2 are each independently a substituted or unsubstituted 1 to 20 alkyl group, a substituted or unsubstituted 6 to 30 aryl group,

Ar1 and Ar2 are each independently selected from the group consisting of a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,

m and n are integers of 0-3, respectively, and the sum of m and n is an integer of 1, 2, 3.

According to an embodiment of the present invention, in formulas (1) to (5), the substituents of ICbz1, ICbz2, Ar1, Ar2, R1 and R2 may be a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro A group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, One or more selected from the group consisting of a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In addition, according to another embodiment of the present invention, the substituents of the ICbz1, ICbz2, Ar1, Ar2, R1 and R2 may be bonded to each other to form a saturated or unsaturated ring, or may be attached or fused together by a pendant method. .

The present invention, in order to achieve the second technical problem, an anode; Cathode; And it provides an organic electroluminescent device having a layer comprising an indolocarbazole derivative represented by the formula (1) interposed between the anode and the cathode.

According to an embodiment of the present invention, the anode and the cathode further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer The indolocarbazole derivative may be included in the light emitting layer between the anode and the cathode, and the thickness of the light emitting layer is preferably 50 to 2,000 Pa.

By using the indolocarbazole derivative according to the present invention, it is possible to provide an organic light emitting device having a low driving voltage and excellent luminous efficiency.

1A to 1F are cross-sectional views illustrating a laminated structure of organic light emitting diodes according to an exemplary embodiment of the present invention.

The present invention is a derivative having the basic skeleton of the indolocarbazole represented by the above [Formula 1] can be effectively used in all layers of the organic field device, especially when employed as a light emitting layer host, holes and electrons are easy to move, Since the electron balance can be maintained, exciton formation can be maximized in the emission layer.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like. Halogen atom, hydroxy group, nitro group, cyano group, silyl group (in this case referred to as "alkylsilyl group"), substituted or unsubstituted amino group (-NH2, -NH (R), -N (R ') (R' '), R' and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, in this case referred to as an" alkylamino group "), a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 20 carbon atoms, Halogenated alkyl group of 1 to 20 carbon atoms, alkenyl group of 1 to 20 carbon atoms, alkynyl group of 1 to 20 carbon atoms, heteroalkyl group of 1 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, aralkyl group of 6 to 20 carbon atoms, carbon number 6 to 20 heteroaryl group or 6 to 20 carbon atoms It may be substituted with an alkyl group Le.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the alkyl group.

The aryl group used in the compound of the present invention means an aromatic system including one or more rings, and the rings may be attached or fused together by a pendant method. The aryl group also includes non-condensed aromatic groups. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, chrysenyl, and fluoranthenyl, and examples of the non-condensed aromatic group include biphenyl group, terphenyl group, and the like. Corresponding. At least one hydrogen atom of the aryl group may be substituted with the same substituent as in the alkyl group (for example, "arylamino group" when substituted with an amino group, "arylsilyl group" when substituted with a silyl group, oxy When substituted with a group, referred to as an "aryloxy group".

The heteroaryl group which is a substituent used in the compound of the present invention means a ring aromatic system having 3 to 30 carbon atoms containing 1, 2 or 3 hetero atoms selected from N, O or S, and the remaining ring atoms are carbon. Can be attached together in a pendant manner. When the heteroaryl group is fused with an aryl group or another heteroaryl group, it is called a condensed aromatic heterocycle, and the heteroaryl group includes a condensed aromatic heterocycle. Specific examples of the heteroaryl group include pyrrole group, furan group, thiophene group, bithiophene group, terthiophene group, pyrazole group, imidazole group, triazole group, isoxazole group, oxazole group, oxadiazole group, pyridine group, di Pyridyl group, terpyridine group, pyridazine group, pyrimidine group, pyrazine group, triazine group, indole group, carbazole group, dibenzoazine group, azaandrodol group, indolocarbazole group, benzofuran group, dibenzofuran group, Thianaphthene group (thianaphthene), dibenzothiophene group, indazole group, benzimidazole group, imidazopyridine group, benzotriazole group, benzothiazole group, benzothiadiazole group, triazolopyrimidine group, purine group, quinoline group , Benzoquinoline group, acridine group, isoquinoline group, phenanthroline group, phthalazine group, quinazoline group, phenoxaline group, phenazine group, phenanthroline group, phenoxazine group and the like.

At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the alkyl group.

Indolocarbazole derivatives according to an embodiment of the present invention may be, for example, any one compound selected from the group represented by the following formula [SPH01] to [SPH106], but is not limited to these exemplary compounds.

[SPH01] [SPH02] [SPH03]

[SPH04] [SPH05] [SPH06]

[SPH07] [SPH08] [SPH09]

[SPH10] [SPH11]

[SPH12] [SPH13]

[SPH14] [SPH15]

[SPH16] [SPH17]

[SPH18] [SPH19]

[SPH20] [SPH21]

[SPH22] [SPH23]

[SPH24] [SPH25] [SPH26]

[SPH27] [SPH28] [SPH29]

[SPH30] [SPH31] [SPH32]

[SPH33] [SPH34]

[SPH35] [SPH36] [SPH37] [SPH38]

[SPH39] [SPH40] [SPH41]

[SPH42] [SPH43]

[SPH44] [SPH45]

[SPH46] [SPH47]

[SPH48] [SPH49]

[SPH50] [SPH51]

[SPH52] [SPH53]

[SPH54] [SPH55]

[SPH56] [SPH57]

[SPH58] [SPH59]

[SPH60] [SPH61]

[SPH62] [SPH63]

[SPH64] [SPH65]

[SPH66] [SPH67] [SPH68] [SPH69]

[SPH70] [SPH71] [SPH72]

[SPH73] [SPH74] [SPH75] [SPH76]

[SPH77] [SPH78] [SPH79] [SPH80]

[SPH81] [SPH82] [SPH83] [SPH84]

[SPH85] [SPH86] [SPH87] [SPH88]

[SPH89] [SPH90] [SPH91] [SPH92]

[SPH93] [SPH94]

[SPH95] [SPH96]

[SPH97] [SPH98]

[SPH99] [SPH100]

[SPH101] [SPH102]

[SPH103] [SPH104]

[SPH105] [SPH106]

The present invention, in order to achieve the second technical problem, an anode; Cathode; And it provides an organic electroluminescent device having a layer comprising an indolocarbazole derivative represented by the above [Formula 1] interposed between the anode and the cathode.

Referring to the organic light emitting device according to the present invention in more detail, the organic light emitting device comprises at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer between the anode and the cathode. The hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer may further increase the probability of light emitting coupling in the light emitting layer by efficiently transferring holes or electrons to the light emitting layer.

The hole injection layer and the hole transport layer are laminated to facilitate the injection of holes from the anode and the transport of the injected holes. As the material for the hole transport layer, electron donor molecules having small ionization potential are used. Diamine, triamine or tetraamine derivatives based on amines are frequently used. In the present invention, as the material of the hole transport layer, as long as it is commonly used in the art, various materials can be used without limitation, for example, N, N'-bis (3-methylphenyl) -N, N '-Diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD ) Can be used. In addition, a hole injection layer (HIL) may be further stacked below the hole transport layer, and the hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. For example, CuPc or Starburst type amines such as TCTA, m-MTDATA, IDE406 (manufactured by Idemitsu Corp.) and the like can be used.

CuPc TCTA

      m-MTDATA

An organic light emitting layer is stacked on the hole transport layer, and the organic light emitting layer may be made of a single material or may be made of a host / dopant.

In general, when the compound is used as a single material, a host / dopant-based light emitting layer is preferable, because an intermolecular interaction generates a mound peak at long wavelengths, resulting in poor color purity, and low efficiency due to a light emission decay effect. The indolocarbazole derivative may be used as a host material in the host / dopant light emitting layer. In the host / dopant light emitting layer, a host material generally uses CBP (4,4'-dicarbazolyl-1,1'-biphenyl), and a dopant material uses Ir (ppy) 3 a lot, but is generally used in the art. It is not particularly limited as long as it is used as. The electron transport layer serves to increase the chance of recombination in the light emitting layer by smoothly transporting electrons supplied from the cathode to the light emitting layer and suppressing movement of holes that are not bonded in the light emitting layer. Such electron transport layer material is not particularly limited as long as it is a material used in the art, for example, Alq 3 (tri-8-hydroxyquinoline aluminum), PBD (2- (4-biphenylyl) -5- ( 4-t-butylphenyl) -1,3,4-oxadiazole), TNF (2,4,7-trinitro fluorenone), BMD, BND and the like can be used.

Meanwhile, an electron injection layer (EIL), which facilitates electron injection from the cathode and ultimately improves power efficiency, may be further stacked on the electron transport layer. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li2O, BaO.

Furthermore, in addition to the above-described hole injection layer, hole transport layer, electron transport layer, and electron injection layer, the organic light emitting device according to the present invention may further include additional functional laminated structures such as a hole blocking layer or an electron blocking layer. . At this time, the hole blocking layer serves to prevent such a problem by using a material having a very low HOMO level because the life and efficiency of the device is reduced when holes are introduced into the cathode through the organic light emitting layer. The material constituting the hole blocking layer is not particularly limited, but must have an ionization potential higher than that of the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

More specifically, FIGS. 1A to 1F illustrate organic light emitting diodes having various types of stacked structures. Referring to this, the organic light emitting diode of FIG. 1A includes an anode / hole injection layer / light emitting layer / cathode. The organic electroluminescent device of FIG. 1B has a structure consisting of an anode / hole injection layer / light emitting layer / electron injection layer / cathode. In addition, the organic light emitting display device of FIG. 1c has a structure of an anode / hole injection layer / hole transporting layer / light emitting layer / cathode, and the organic light emitting device shown in FIG. 1d includes an anode / hole injection layer / hole transporting layer / light emitting layer / electron injection. The organic electroluminescent device of FIG. 1E has a structure of a layer / cathode, and has an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode. Finally, the organic electroluminescent device of FIG. 1F is an anode. It has a structure of / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

The organic electroluminescent device according to the present invention may include the indolocarbazole derivative in various laminated structures interposed between the anode and the cathode. Preferably, the indolocarbazole derivative is a light emitting layer between the anode and the cathode. Can be used as host material in

In addition, the thickness of the light emitting layer including the indolocarbazole derivative may be 50 to 2,000 kPa, but when the thickness is less than 50 kPa, the luminous efficiency is lowered, and when it exceeds 2,000 kPa, the driving voltage is uneconomical. to be.

A method of manufacturing an organic light emitting display device according to the present invention will be described with reference to FIGS. 1A to 1F.

First, an anode material is coated on the substrate. As the substrate, a substrate used in a conventional light emitting device is used. A glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, as the anode material, materials commonly used in the art, such as transparent and highly conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), or zinc oxide (ZnO), may be used. . A hole injection layer is stacked on the anode, and then a hole transport layer is formed on the hole injection layer.

Next, after the light emitting layer is laminated on the hole transport layer, a hole blocking layer is selectively formed thereon. Finally, after the electron transport layer is laminated on the hole blocking layer, the electron injection layer may be selectively formed, and the organic light emitting diode according to the present invention may be manufactured by vacuum thermal depositing a metal for forming a cathode on the electron injection layer. Will be. Lamination of the organic layer is performed by one or more methods selected from the methods of vacuum thermal deposition, spin coating or inkjet printing.

On the other hand, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminium-lithium-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), Magnesium-silver (Mg-Ag) or the like may be used, and a transmissive cathode using ITO or IZO may be used to obtain a front light emitting device.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by [SPH16]

(1) Synthesis of Compound Represented by [Formula 1-a]

The compound represented by [Formula 1-a] was synthesized by the following [Scheme 1].

Scheme 1

[Formula 1-a]

In a 1000 ml round bottom flask was placed 30.0 g (0.093 mol) of N-phenyl-3-bromo carbazole and 300 ml of tetrahydrofuran under nitrogen. Lowered to -73 ° C, and 70 ml of normal-butyllithium was added dropwise, and when the dropwise addition was completed, the mixture was stirred at low temperature for 1 hour, then raised to room temperature, and stirred for 2 hours. Lowered to −73 ° C. and 14 ml of trimethylborate was added dropwise. After raising to room temperature, 50 ml of 2M aqueous hydrochloric acid solution was added dropwise. Extraction with ethyl acetate and water and concentration of the organic layer under reduced pressure and recrystallization from hexane yielded 20 g of a compound represented by [Formula 1-a]. (Yield: 74.8%)

(2) Synthesis of Compound Represented by [Formula 1-b]

The compound represented by [Formula 1-b] was synthesized by the following [Scheme 2].

Scheme 2

[Formula 1-b]

In a 500 mL round bottom flask, 20.0 g (0.07 mol) of compound [Formula 1-a], 16.9 g (0.084 mol) of 2-bromonitrobenzene, 1.6 g (0.002 mol) of Pd [PPh ₃ ] ₄ , 19.3 g of potassium carbonate ( 0.139 mol), 120 ml of tetrahydrofuran, 120 ml of 1,4-dioxane and 40 ml of water were added, and the mixture was refluxed at 80 ° C for 12 hours. After the reaction was completed, 300 ml of ethyl acetate and 100 ml of distilled water were used for extraction. After repeating twice, the organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from methylene chloride and hexane to obtain 22 g of a compound represented by [Formula 1-b]. (Yield: 86.7%)

(3) Synthesis of Compound Represented by [Formula 1-c]

The compound represented by [Formula 1-c] was synthesized by the following [Scheme 3].

Scheme 3

[Formula 1-c]

22.0 g (0.060 mol) of [Formula 1-b], 39.6 g (0.15 mol) of triphenylphosphine, and 220 ml of dichlorobenzene were added to a 500 mL round bottom flask, and the mixture was refluxed at 160 ° C. for 12 hours. After the reaction was completed, the mixture was filtered while hot and extracted using methylene chloride and distilled water. After repeating twice, the organic layer was concentrated under reduced pressure, and methylene chloride and hexane were column chromatographed with a developing solvent to obtain 16.4 g of the compound represented by [Formula 1-c]. (Yield: 81.7%)

(4) Synthesis of Compound Represented by [Formula 1-d]

The compound represented by [Formula 1-d] was synthesized by the following [Scheme 4].

Scheme 4

[Formula 1-d]

15.0 g (0.045 mol) iodobenzene, 12.5 g (0.9 mol) potassium carbonate, 6.7 g (0.068 mol) copper chloride, 150 ml dimethyl sulfoxide in a 250 ml round bottom flask At reflux. After the reaction was completed, 300 ml of methylene chloride and 100 ml of distilled water were used for extraction. The organic layer was concentrated under reduced pressure, an excess of hexane was added to give an impure product, and the residue was purified by column chromatography with methylene chloride: hexane = 1: 10 developing solvent to obtain 14.3 g of the compound represented by [Formula 1-d]. (Yield: 77.6%)

(5) Synthesis of Compound Represented by [Formula 1-e]

The compound represented by [Formula 1-e] was synthesized by the following [Scheme 5].

Scheme 5

[Formula 1-e]

14.3 g (0.035 mol) of Compound [Formula 1-d] and 80 ml of tetrahydrofuran were dissolved in a 500 ml round bottom flask, and 6.2 g of N-bromosuccinimide was dissolved in 40 ml of tetrahydrofuran, and the mixture was stirred for 3 hours. When the reaction was completed, 100 ml of distilled water was added to the reaction solution to precipitate a solid. The solid was filtered and recrystallized with methylene chloride and hexane to obtain 16.0 g of the compound represented by [Formula 1-e]. (Yield: 93.8%)

(6) Synthesis of Compound Represented by Formula 1-f

The compound represented by [Formula 1-f] was synthesized by the following [Scheme 6].

Scheme 6

[Formula 1-f]

In a 250 mL round bottom flask, 16.0 g (0.033 mol), bis (pinacolato) diboron 10.0g (0.039 mol), 0.8 g (0.001 mol) PdCl ₂ (dppf), 7.5 g of potassium acetate ( 0.098 mol) and 160 ml of toluene were added and stirred for 8 hours. After the reaction was completed, the mixture was filtered under hot state, concentrated under reduced pressure, methylene chloride and hexane were purified by column chromatography with a developing solvent to obtain 12.0 g of the compound represented by [Formula 1-f]. (Yield: 68.4%)

(7) Synthesis of Compound Represented by [SPH16]

The compound represented by [SPH16] was synthesized according to Reaction Scheme 7 below.

Scheme 7

[SPH16]

In a 250 mL round bottom flask, 12.0 g (0.022 mol), 2,6-dibromopyridine 2.6 g (0.011 mol), Pd (PPh ₃ ) ₄ 1.0 g (0.001 mol), potassium carbonate 12.4 g (0.09 mol), 70 ml of tetrahydrofuran, 70 ml of 1,4-dioxane and 24 ml of water were added to reflux. After the reaction was completed, the mixture was extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure, and methylene chloride and hexane were purified by column chromatography with a developing solvent to obtain 4.8 g of the compound represented by [SPH16]. (Yield: 47.9%)

MS (MALDI-TOF): m / z = 891.34 [M] ⁺

Elemental analysis (EA): theoretical value-C. 87.52%; H. 4.63%; N. 7.85%

Found-C. 87.46%; H. 4.58%; N. 7.96%

Synthesis Example 2 Synthesis of Compound Represented by [SPH21]

(1) Synthesis of Compound Represented by [Formula 2-a]

The compound represented by [Formula 2-a] was synthesized by the following [Scheme 8].

Scheme 8

[Formula 2-a]

10.0 g (0.030 mol) of 3-methyliodobenzene, 8.3 g (0.6 mol) of potassium carbonate, 4.5 g (0.045 mol) of copper chloride, dimethyl in a 250 ml round bottom flask It was refluxed in 100 ml of sulfoxide. After the reaction was completed, 300 ml of methylene chloride and 100 ml of distilled water were used for extraction. The organic layer was concentrated under reduced pressure, hexane was added to give an impure product, and column chromatography was performed with methylene chloride: hexane = 1: 10 developing solvent to obtain 8.2 g of the compound represented by [Formula 2-a]. (Yield 66.7%)

(2) Synthesis of Compound Represented by [Formula 2-b]

The compound represented by [Formula 2-b] was synthesized by the following [Scheme 9].

Scheme 9

[Formula 2-b]

In a 250 ml round bottom flask, 8.1 g (0.019 mol) of compound [Formula 2-a] and tetrahydrofuran were dissolved in 80 ml, and 3.4 g of N-bromosuccinimide was dissolved in 20 ml dropwise and stirred for 3 hours. When the reaction was completed, 100 ml of distilled water was added to the reaction solution to precipitate a solid. The solid was filtered and recrystallized with methylene chloride and hexane to obtain 8.1 g of the compound represented by [Formula 2-b]. (Yield 84.3%)

(3) Synthesis of Compound Represented by [Formula 2-c]

The compound represented by [Formula 2-c] was synthesized by the following [Scheme 10].

Scheme 10

[Formula 2-c]

8.1g (0.016mol) bis (pinacolato) diboron 4.9g (0.019mol), PdCl ₂ (dppf) 0.4g (0.001mol), potassium acetate 3.7g (250g) in a 250mL round bottom flask 0.048 mol) and 80 ml of toluene were added and stirred for 6 hours. After the reaction was completed, the mixture was filtered while hot, concentrated under reduced pressure, and methylene chloride and hexane were subjected to column chromatography with a developing solvent to obtain 7.2 g of [Formula 2-c]. (Yield: 83.4%)

(4) Synthesis of Compound Represented by [SPH21]

The compound represented by [SPH21] was synthesized according to Reaction Scheme 11 below.

Scheme 11

[SPH21]

7.2 g (0.013 mol), dichlorophenyltriazine 1.5 g (0.006 mol), Pd (PPh ₃ ) ₄ 0.6 g (0.001 mol), potassium carbonate 7.4 g (0.054 mol) in a 250 mL round bottom flask 50 ml of tetrahydrofuran, 50 ml of 1,4-dioxane and 15 ml of water were added and refluxed. After the reaction was completed, the mixture was extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure, and methylene chloride and hexane were purified by column chromatography with a developing solvent to obtain 3.6 g of the compound represented by [SPH21]. (Yield: 59.9%)

MS (MALDI-TOF): m / z = 997.39 [M] ⁺

Elemental analysis (EA): theoretical value-C. 85.43%; H. 4.75%; N. 9.82%

Found-C. 85.63%; H. 4.57%; N. 9.84%

Synthesis Example 3 Synthesis of Compound Represented by [SPH23]

[SPH23] is represented by the same method as the synthesis method of Synthesis Example 2, except that 3- (3-bromophenyl) pyridine is used instead of 3-methyliodobenzene in [Scheme 8] of Synthesis Example 2. To obtain a compound.

MS (MALDI-TOF): m / z = 1123.41 [M] ⁺

Elemental analysis (EA): theoretical value-C. 84.39%; H. 4.39%; N. 11.21%

Found-C. 84.64%; H. 4.44%; N. 10.91%

Synthesis Example 4 Synthesis of Compound Represented by [SPH25]

In Scheme 7 of Synthesis Example 1, N- [4- (4,6-dichloropyrimidin-2-yl) phenyl] -N-phenylpyridin-3-amine was substituted for 2,6-dibromopyridine. Except for the use, the compound represented by [SPH25] was obtained by the same method as the synthesis method of Synthesis Example 1.

MS (MALDI-TOF): m / z = 1136.43 [M] ⁺

Elemental analysis (EA): theoretical value-C. 85.54%; H. 4.61%; N. 9.85%

Found-C.85.31%; H. 4.61%; N. 10.08%

Synthesis Example 5 Synthesis of Compound Represented by [SPH28]

Synthesis Example 1 except that 6- [3- (4,6-dichloropyrimidin-2-yl) phenyl] quinoline was used instead of 2,6-dibromopyridine in [Scheme 7] of Synthesis Example 1 The compound represented by [SPH28] was obtained by the same method as the synthesis method of 1.

MS (MALDI-TOF): m / z = 1095.4 [M] ⁺

Elemental analysis (EA): theoretical value-C. 86.55%; H. 4.51%; N. 8.94%

Found-C. 86.14%; H. 4.72%; N. 9.14%

<Examples 1 to 5> Preparation of an organic electroluminescent device comprising a compound synthesized in Synthesis Examples 1 to 5

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the ITO glass in a vacuum chamber, the base pressure was 1 × 10 ⁻⁶ torr, and then DNTPD (700 kPa) and NPD (300 kPa) were deposited on the ITO, respectively. The film was formed in the order of Ir (ppy) ₃ (10%) (300kW), Alq ₃ (350kW), LiF (5kW), and Al (1,000kW) and measured at 0.4mA.

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

Comparative Example

The organic light emitting display device for the comparative example was manufactured in the same manner except that CBP was used instead of the compound prepared by the present invention as a host material in the device structure of the above embodiment.

[CBP]

division Host Dopant Doping Concentration (%) ETL V ㏅ / A COLOR Comparative Example 1 CBP Ir (ppy) ₃ 10 Alq ₃ 7.2 36.24 green Example 1 SPH16 Ir (ppy) ₃ 10 Alq ₃ 3.52 38.0 green Example 2 SPH21 Ir (ppy) ₃ 10 Alq ₃ 5.72 39.89 green Example 3 SPH23 Ir (ppy) ₃ 10 Alq ₃ 4.04 37.22 green Example 4 SPH25 Ir (ppy) ₃ 10 Alq ₃ 5.27 42.07 green Example 5 SPH28 Ir (ppy) ₃ 10 Alq ₃ 4.57 36.13 green

From the results of <Examples 1 to 5>, <Comparative Example 1> and [Table 1], an organic electroluminescent device comprising an indolocarbazole derivative according to the present invention as a host material is an organic field in which the host material is CBP Since the driving voltage is lower than that of the light emitting device, and the light emitting efficiency such as current efficiency is excellent, it can be seen that it can be usefully used for a display device, a display device and an illumination.

Claims (8)

Indolocarbazole derivatives of Formula 1 below:
[Formula 1]

In [Formula 1],
ICbz1 and ICbz2 are each independently selected from the structures represented by the following [Formula 2] to [Formula 6],

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6]
In this case, R1 and R2 are each independently a substituted or unsubstituted 1 to 20 alkyl group, a substituted or unsubstituted 6 to 30 aryl group,
Ar1 and Ar2 are each independently selected from the group consisting of a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
m and n are integers of 0-3, respectively, and the sum of m and n is an integer of 1, 2, 3. The method of claim 1,
The substituents of ICbz1, ICbz2, Ar1, Ar2, R1 and R2 may be a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 to 30 Alkoxy group of 30, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted carbon atoms 1 to 30 At least one selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms Indolocarbazole derivatives. The method of claim 2,
Substituents of the ICbz1, ICbz2, Ar1, Ar2, R1 and R2 are bonded to each other to form a saturated or unsaturated ring, indolocarbazole derivatives, characterized in that attached or fused together by a pendant method. The method of claim 1,
Indolocarbazole derivatives, characterized in that any one compound selected from the group represented by the formula [SPH01] to [SPH106]:
[SPH01] [SPH02] [SPH03]

[SPH04] [SPH05] [SPH06]

[SPH07] [SPH08] [SPH09]

[SPH10] [SPH11]

[SPH12] [SPH13]

[SPH14] [SPH15]

[SPH16] [SPH17]

[SPH18] [SPH19]

[SPH20] [SPH21]

[SPH22] [SPH23]

[SPH24] [SPH25] [SPH26]

[SPH27] [SPH28] [SPH29]

[SPH30] [SPH31] [SPH32]

[SPH33] [SPH34]

[SPH35] [SPH36] [SPH37] [SPH38]

[SPH39] [SPH40] [SPH41]

[SPH42] [SPH43]

[SPH44] [SPH45]

[SPH46] [SPH47]

[SPH48] [SPH49]

[SPH50] [SPH51]

[SPH52] [SPH53]

[SPH54] [SPH55]

[SPH56] [SPH57]

[SPH58] [SPH59]

[SPH60] [SPH61]

[SPH62] [SPH63]

[SPH64] [SPH65]

[SPH66] [SPH67] [SPH68] [SPH69]

[SPH70] [SPH71] [SPH72]

[SPH73] [SPH74] [SPH75] [SPH76]

[SPH77] [SPH78] [SPH79] [SPH80]

[SPH81] [SPH82] [SPH83] [SPH84]

[SPH85] [SPH86] [SPH87] [SPH88]

[SPH89] [SPH90] [SPH91] [SPH92]

[SPH93] [SPH94]

[SPH95] [SPH96]

[SPH97] [SPH98]

[SPH99] [SPH100]

[SPH101] [SPH102]

[SPH103] [SPH104]

[SPH105] [SPH106]

Anode;
Cathode; And
An organic electroluminescent device having a layer interposed between the anode and the cathode and comprising the indolocarbazole derivatives of claims 1 to 4. The method of claim 5, wherein
An organic electroluminescent device further comprising one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and an electron blocking layer between the anode and the cathode. The method according to claim 6,
The indolocarbazole derivative is an organic electroluminescent device, characterized in that contained in the light emitting layer between the anode and the cathode. The method of claim 7, wherein
The thickness of the light emitting layer is an organic light emitting device, characterized in that 50 to 2,000 kPa.

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