KR101729660B1 - Novel compoung for organic electroluminescent device, organic electroluminescent device including the same and electric apparatus - Google Patents

Abstract

상기 식에서, R1, R2, L1, L2, X 및 Het는 명세서에서 정의한 바와 같다. 1. An organic electroluminescent device compound represented by the following formula (1): < EMI ID =
&Lt; Formula 1 &gt;

Wherein R1, R2, L1, L2, X and Het are as defined in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound for organic electroluminescent devices, an organic electroluminescent device including the compound, and an electronic device using the same. BACKGROUND ART &lt; RTI ID = 0.0 &gt;

The present invention relates to a novel compound for an organic electroluminescent device, an organic electroluminescent device including the compound and an electronic device.

An electroluminescence device (EL device) is a self-emissive type display device having a high response speed and a wide viewing angle. In 1987, Eastman Kodak Company first developed an organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer material [Appl. Phys. Lett. 51, 913, 1987].

The most important factor for determining the luminous efficiency in an OLED is a luminescent material, and a phosphorescent material in a luminescent material can improve luminous efficiency up to 4 times the theoretical value of a fluorescent material. Until now, iridium (III) complexes and carbazole-based materials have been widely known as phosphorescent materials, and new phosphorescent materials are being studied in recent years.

The principle of the organic electroluminescent phenomenon is that when a voltage is applied between two electrodes when an organic material layer exists between the cathode and the anode, electrons and holes are injected into the organic material layer from the cathode and the anode, respectively. Electrons and holes injected into the organic layer are recombined to form an exciton, and the exciton falls back to the ground state to emit light. An organic electroluminescent device using this principle can be generally constituted of an organic material layer including a cathode, an anode and an organic material layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

Most of materials used in organic electroluminescent devices are pure organic materials or complexes in which an organic material and a metal form a complex with each other. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, Can be distinguished. As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material which is easily oxidized and electrochemically stable at the time of oxidation, is mainly used. On the other hand, as an electron injecting material and an electron transporting material, an organic material having an n-type property, that is, an organic material which is easily reduced and electrochemically stable at the time of reduction is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable state in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable. Accordingly, there is a need in the art to develop new organic materials having the above-described requirements.

One embodiment of the present invention provides a compound for an organic electroluminescent device having an appropriate energy level, electrochemical stability, and thermal stability.

Another embodiment of the present invention provides an organic electroluminescent device comprising the compound for an organic electroluminescent device.

Another embodiment of the present invention provides an electronic apparatus to which the organic electroluminescent device is applied.

In one embodiment of the present invention, there is provided an organic electroluminescent device compound represented by the following general formula (1).

&Lt; Formula 1 >

In this formula,

, 스피로 구조로 결합된 치환 또는 비치환된 C6-C50의 아릴기, 스피로 구조로 결합된 치환 또는 비치환된 C5-C50의 사이클로알킬기이고, 상기 아릴기 및 상기 사이클로알킬기가 2개 이상의 치환기를 가지는 경우 상기 2개 이상의 치환기가 융합되어 다환의 지방족 또는 방향족 융합고리를 형성할 수 있고;X is C (R15) (R16), C (CH 3) 2, C = O, O, S, N (R17), Si (CH 3) 2, SO 2, Se,

, A substituted or unsubstituted C6-C50 aryl group bonded with a spiro structure, a substituted or unsubstituted C5-C50 cycloalkyl group bonded with a spiro structure, and the aryl group and the cycloalkyl group have two or more substituents The two or more substituents may be fused to form a polycyclic aliphatic or aromatic fused ring;

Substituted or unsubstituted C7-C50 arylalkyl group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7-C50 arylalkyl group, a substituted or unsubstituted C7- A substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, a substituted or unsubstituted C1-C50 cycloalkyl group, a substituted or unsubstituted C6- A substituted or unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;

R15 and R16 may be fused together to form a polycyclic aliphatic or aromatic fused ring;

Het is a substituted or unsubstituted C3-C60 heteroaryl group or a substituted and unsubstituted C4-C60 heteroarylalkyl group and at least one heteroatom selected from B, N, O, S, P (= O) Atoms;

L1 and L2 are each independently a single bond, a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C7-C50 arylalkylene group, a substituted or unsubstituted C6-C50 cycloalkylene group, A substituted or unsubstituted C1-C50 alkenyl group, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C3-C50 heteroarylene group, a substituted or unsubstituted C4-C50 heteroarylalkylene group, C6-C50 arylimino group, a substituted or unsubstituted C7-C50 arylalkylimino group, or a substituted or unsubstituted C7-C50 arylalkoxyimino group.

In another embodiment of the present invention, there is provided an organic electroluminescent device including a structure in which a first electrode, one or more organic material layers and a second electrode are stacked, and the organic material layer includes at least one compound for the organic electroluminescent device do.

In another embodiment of the present invention, there is provided an electronic device including the organic electroluminescent device.

The compound for an organic electroluminescent device can satisfactorily satisfy conditions required for a material usable in an organic electroluminescent device, for example, an appropriate energy level, an electrochemical stability, and a thermal stability. It can play various roles as required.

Fig. 1 shows the 1H-NMR measurement results of the compound 119 prepared in Example 1. Fig.
2 is a TGA measurement result of the compound 119 prepared in Example 1. Fig.
3 shows the results of DSC measurement of the compound 119 prepared in Example 1. Fig.
4 is a UV absorption spectrum of the compound 119 prepared in Example 1. Fig.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In one embodiment of the present invention, there is provided an organic electroluminescent device compound represented by the following general formula (1).

&Lt; Formula 1 >

In this formula,

, 스피로 구조로 결합된 치환 또는 비치환된 C6-C50의 아릴기, 스피로 구조로 결합된 치환 또는 비치환된 C5-C50의 사이클로알킬기이고, 상기 아릴기 및 상기 사이클로알킬기가 2개 이상의 치환기를 가지는 경우 상기 2개 이상의 치환기가 융합되어 다환의 지방족 또는 방향족 융합고리를 형성할 수 있고;X is C (R15) (R16), C (CH 3) 2, C = O, O, S, N (R17), Si (CH 3) 2, SO 2, Se,

, A substituted or unsubstituted C6-C50 aryl group bonded with a spiro structure, a substituted or unsubstituted C5-C50 cycloalkyl group bonded with a spiro structure, and the aryl group and the cycloalkyl group have two or more substituents The two or more substituents may be fused to form a polycyclic aliphatic or aromatic fused ring;

Substituted or unsubstituted C7-C50 arylalkyl group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7-C50 arylalkyl group, a substituted or unsubstituted C7- A substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, a substituted or unsubstituted C1-C50 cycloalkyl group, a substituted or unsubstituted C6- A substituted or unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;

R15 and R16 may be fused together to form a polycyclic aliphatic or aromatic fused ring;

Het is a substituted or unsubstituted C3-C60 heteroaryl group or a substituted and unsubstituted C4-C60 heteroarylalkyl group and at least one heteroatom selected from B, N, O, S, P (= O) Atoms;

L1 and L2 are each independently a single bond, a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C7-C50 arylalkylene group, a substituted or unsubstituted C6-C50 cycloalkylene group, A substituted or unsubstituted C1-C50 alkenyl group, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C3-C50 heteroarylene group, a substituted or unsubstituted C4-C50 heteroarylalkylene group, C6-C50 arylimino group, a substituted or unsubstituted C7-C50 arylalkylimino group, or a substituted or unsubstituted C7-C50 arylalkoxyimino group.

R2 is defined as the case where the bonding position is not specified in the formula (1), and when R2 is absent, R2 is hydrogen.

The compound for an organic electroluminescent device can satisfactorily satisfy conditions required for a material usable in an organic electroluminescent device, for example, appropriate energy level, electrochemical stability, and thermal stability. And thus can play various roles required in an organic electroluminescent device.

The structure represented by the above formula (1) is a structure in which a Het group, phenylene having an R 1 substituent, and three fused ring groups are linked by a linker group of L 1 and L 2, wherein the three fused ring groups are bonded to each other through a pentagonal ring And the carbon closest to X in the hexagonal ring fused to the carbon atom is defined as the first carbon atom, the carbon atom at the second carbon atom is bonded to the carbon atom at the second carbon atom, . &Lt; / RTI &gt;

In addition, when R1 is not hydrogen, it is possible to form a structure in which three bonds are present in the benzene ring of the phenylene having the R1 substituent, and such a structure has an appropriate energy level as described above, excellent electrochemical stability and excellent May be more helpful in improving the properties of thermal stability.

Such a structure of the compound for an organic electroluminescence device can be usefully applied as a light emitting layer material.

In one embodiment, the compound for an organic electroluminescent device may be included as a phosphorescent host, a fluorescent host, a phosphorescent dopant, or a fluorescent dopant material in a light emitting layer.

In the present specification, the substituent in the case of "substituted", unless otherwise defined, includes a C1-C50 alkyl group, a C3-C50 cycloalkyl group, a C2-C50 alkenyl group, a C3-C50 cycloalkenyl group, A C5-C50 cycloalkynyl group, a cyano group, a C1-C20 alkoxy group, a C6-C60 aryl group, and a C7-C60 arylalkyl group, and combinations thereof &Lt; / RTI &gt; is substituted with two or more substituents of

In another embodiment, the compound represented by Formula 1 may be any of the compounds represented by Formulas 2 to 4 below.

[Chemical Formula 2] &lt; EMI ID = [Chemical Formula 4]

In this formula,

A is carbon or nitrogen;

R1 to R4 each independently represent hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7-C50 arylalkyl group, a substituted or unsubstituted C4- A substituted or unsubstituted C1-C50 alkylamino group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, Or an unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;

X, L 1 and L 2 are as defined in the above formula (1).

Specifically, the compound represented by the formula (1) may be any one of the compounds represented by the following formulas (5) to (20).

[Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8]

[Chemical Formula 11] [Chemical Formula 11] [Chemical Formula 12]

[Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16]

[Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20]

In this formula,

A is carbon or nitrogen;

R 1 to R 10 are each independently selected from the group consisting of hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C 1 -C 50 alkyl group, a substituted or unsubstituted C 7 -C 50 arylalkyl group, A substituted or unsubstituted C1-C50 alkylamino group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, Or an unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;

X is as defined in the above formulas (1) to (4).

R 2, R 6, R 7 and R 9 are defined as the case where the bonding position is not specified in formula (1), and when R 2, R 6, R 7 or R 9 is absent, R 2, R 6, R 7 or R 9 is hydrogen.

Specifically, the compound represented by Formula 1 may be any one of compounds represented by the following Chemical Formulas 21 to 47.

[Chemical Formula 21] (23)

[Chemical Formula 24] (26)

[Chemical Formula 27] [Chemical Formula 29]

[Chemical Formula 30] (32)

[Chemical Formula 33] (35)

[Chemical Formula 36] (38)

[Chemical Formula 39] (41)

[Chemical Formula 42] (44)

[Chemical Formula 45] (47)

A is carbon or nitrogen;

R 1 to R 13 are each independently selected from the group consisting of hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C 1 -C 50 alkyl group, a substituted or unsubstituted C 7 -C 50 arylalkyl group, A substituted or unsubstituted C1-C50 alkylamino group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, Or an unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;

X and L &lt; 1 &gt; are the same as defined in the above formula (1).

R2, R6, R7, R9, R12 and / or R13, R9, R12, and R13 are not bonded to each other in formula (1) And R13 is hydrogen.

In the compound represented by the general formula (1), R1, R2, R15, R16 and R17 may be, for example,

Hydrogen (H);

Deuterium (D);

halogen;

C20 alkyl group, C3-C50 cycloalkyl group, C2-C50 alkenyl group, C3-C50 cycloalkenyl group, C2-C50 alkynyl group, C5-C50 cycloalkynyl group, cyano group, C1-C20 A substituted or unsubstituted heteroaryl group substituted with at least one group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group of C6-C60, and an arylalkyl group of C7-C60;

C20 alkyl group, C3-C50 cycloalkyl group, C2-C50 alkenyl group, C3-C50 cycloalkenyl group, C2-C50 alkynyl group, C5-C50 cycloalkynyl group, cyano group, C1-C20 An aryl group of C6-C60, an arylalkyl group of C7-C60, or a heteroarylalkyl group which is unsubstituted or substituted with at least one group selected from the group consisting of C7-C60 arylalkyl groups.

Wherein the heteroaryl group and the heteroarylalkyl group are each independently selected from the group consisting of a heteroatom B, N, O, S, P (O) R, = O), Si and P, as shown in FIG.

In the compound represented by Formula 1, R1, R2, R15, R16 and R17 are each independently hydrogen, a phenyl group, a biphenyl group, a naphthyl group, a carbazole group or a pyridine group, May each independently be a single bond, a phenylene group, a biphenylene group, a naphthylene group, a carbazole group or a pyridine group.

More specifically, the compound represented by Formula 1 may be any one of compounds represented by the following Formulas 101 to 306, but is not limited thereto.

The organic electroluminescence device compound represented by Formula 1 may be synthesized by, for example, reacting Compound A, Compound B and Compound C by the following Reaction Scheme 1 or Reaction Scheme 2.

, 또는

이고,In the above compounds A, B and C, X1 to X5 each independently represent Cl, Br, I, B (OH) ₂ ,

, or

ego,

X, L 1, L 2, R 2 and Het are as defined in the above formula (1).

[Reaction Scheme 1]

[Reaction Scheme 2]

In the above Reaction Schemes 1 and 2,

, 또는

이고,X3 to X6 are Cl, Br, I, B (OH) ₂ or

, or

ego,

X, L 1, L 2, R 1, R 2 and Het are as defined in the above formula (1).

According to another embodiment of the present invention, there is provided an organic electroluminescent device including a structure in which a first electrode, at least one organic material layer and at least one second electrode are stacked, and the organic material layer includes at least one compound represented by Formula 1 do.

The compound represented by Formula 1 contained in the organic layer of the organic electroluminescent device has been described in detail above.

In one embodiment, the organic layer includes a light emitting layer, and the light emitting layer may include a compound represented by the above formula (1).

The compound represented by the formula (1) may be included as a phosphorescent host, a fluorescent host, a phosphorescent dopant, or a fluorescent dopant in the light emitting layer.

The light emitting layer may further include a phosphorescent host, a fluorescent host, a phosphorescent dopant, or a fluorescent dopant material of a known material, in addition to the compound represented by the general formula (1).

The organic material layer may suitably include at least one selected from the group consisting of a hole transporting layer, a hole injecting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer, and an electron blocking layer,

The hole transporting layer, the hole injecting layer, the hole blocking layer, the electron transporting layer, the electron injecting layer, and the electron blocking layer may be formed using known materials, respectively, or may include one or more compounds represented by Formula 1 .

The organic material layer may be produced according to a known manufacturing method of forming or laminating an organic thin film layer.

In another embodiment of the present invention, there is provided an electronic device including the organic electroluminescent device.

The organic electroluminescent device can be applied to various applications. For example, the electronic device to which the organic electroluminescent device is applied may include an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O- LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field-quench device (O-FQD), a luminescent electrochemical cell (LEC), an organic laser diode Device (OLED).

Hereinafter, examples and comparative examples of the present invention will be described. The following embodiments are only examples of the present invention, and the present invention is not limited to the following embodiments.

( Example )

Example  1: Synthesis of compound [119]

The compound represented by the above formula (119) (hereinafter referred to as the compound 119) was prepared according to the following reaction scheme 3.

[Reaction Scheme 3]

Preparation of intermediate compound [119-3]

10.0 g (40.6 mmol) of the compound [119-1], 10.7 g (44.7 mmol) of the compound [119-2], 5.9 g (60.9 mmol) of tetrabutoxy sodium and 150 ml of toluene were placed in a 0.5 L reaction flask under a nitrogen atmosphere Stir at room temperature. 0.1 g (0.4 mmol) of palladium acetate and 0.3 g (0.8 mmol) of trityl butylphosphine (50%) were charged and refluxed under stirring in a nitrogen stream for 15 hours. After completion of the reaction, the mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 9.0 g (69%) of intermediate compound [119-3].

Preparation of intermediate compound [119-4]

In a 0.5 L reaction flask, 10 g (31 mmol) of the compound [119-3] was dissolved in 150 ml of tetrahydrofuran in a nitrogen atmosphere and stirred. Butyllithium (2.5M) was slowly added dropwise at 78 DEG C, and the mixture was slowly stirred at room temperature for 12 hours under a nitrogen stream. After completion of the reaction, a 6N hydrochloric acid aqueous solution was added dropwise to make the reaction solution acidic, and saturated brine was added. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to obtain 7.0 g (78%) of an intermediate compound [119-4] as a pale gray solid.

Preparation of intermediate compound [119-6]

In a 250ml reaction flask, 5.0g (17.4mmol) of the compound [119-4], 7.1g (22.6mmol) of the compound [119-5], 0.6g (0.5mmol) of tetrakis triphenylphosphine palladium (0) 8.5 g (26.1 mmol) of cesium carbonate was dissolved in 120 ml of toluene, 10 ml of ethanol and 20 ml of distilled water were added, and the mixture was refluxed with stirring for 20 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 8.3 g (71%) of intermediate compound [119-6].

Preparation of intermediate compound [119-8]

(4.2 mmol) of the compound [119-6], 2.2 g (5.0 mmol) of the compound [119-7] and 0.4 g (0.4 mmol) of tetrakis triphenylphosphine palladium (0) were placed in a 250 ml reaction flask under a nitrogen atmosphere, 5.8 g (17.9 mmol) of cesium carbonate was dissolved in 120 ml of 1,4-dioxane, 20 ml of distilled water was added, and the mixture was refluxed and stirred for 24 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 2.4 g (41%) of intermediate compound [119-8].

Preparation of compound [119]

(12.0 mmol) of the compound [119-8], 1.4 g (11.3 mmol) of the compound [119-9] and 0.2 g (0.1 mmol) of tetrakis triphenylphosphinevaladium (0) were placed in a 250 ml reaction flask under a nitrogen atmosphere, 2.1 g (6.3 mmol) of cesium carbonate was dissolved in 800 ml of 1,4-dioxane, 160 ml of distilled water was added, and the mixture was refluxed with stirring for 20 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and the solid was filtered under reduced pressure. The obtained solid was washed with methanol, distilled water and acetone, and then recrystallized from tetrahydrofuran and hexane to obtain 2.7 g (91%) of a target compound of a white solid [119] .

^{1 H NMR (400 MHz, THF} -d 8): δ 8.96 (d, 2H), 8.88 (dd, 4H), 8.33 (d, 1H), 8.24 (d, 1H), 8.03 (d, 3H), 7.98 (m, 3H), 7.48-7.40 (m, 3H), 7.40-7.30 (m, 3H) (m, 1 H)

MS / FAB: 322 (M ^&lt; ^{+ &} gt ^; ).

1 is a 1 H-NMR spectrum of the compound 119.

Example  2

Compound 132 (hereinafter referred to as Compound 132) was prepared by changing only the substituent in the same manner as in Example 1.

Example  3

Compound 163 (hereinafter referred to as Compound 163) was prepared in the same manner as in Example 1 except that only the substituent was changed.

Example  4

Compound 175 (hereinafter referred to as Compound 175) was prepared in the same manner as in Example 1 except that only the substituent was changed.

Example  5

Compound 186 (hereinafter referred to as Compound 186) was prepared by changing only the substituent in the same manner as in Example 1.

Example  6

Compound 216 (hereinafter referred to as Compound 216) was prepared by changing only the substituent in the same manner as in Example 1.

Example  7

Compound 235 (hereinafter referred to as Compound 235) was prepared by changing only the substituent in the same manner as in Example 1.

Example  8

Compound (269) (hereinafter referred to as Compound 269) was prepared by changing only the substituent in the same manner as in Example 1.

Example  9

Compound 272 (hereinafter referred to as Compound 272) was prepared by changing only the substituent in the same manner as in Example 1.

Example 10

Compound 299 (hereinafter referred to as Compound 299) was prepared by changing only the substituent in the same manner as in Example 1.

Example  11-20

The following compound D was used as the phosphorescent green dopant and the compound D was used as the phosphorescent green host, respectively, using the compounds 119, 132, 163, 175, 186, 216, 235, 269, 272, NPD (N, N'-di (naphthalene-2-yl) -N-phenylamino) -triphenylamine was used as the hole injection layer material, and TNATA (4,4 ', 4 " 1-yl) -N, N'-diphenylbenzidine was used as a hole transport layer material to fabricate an organic electroluminescent device having the following structure (Examples 11-20, respectively): ITO / 2-TNATA (30 nm) / Alq3 (30 nm) / Liq (1 nm) / Al (100 nm).

The anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TNATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. The compound represented by Formula 1 and Compound D (doping ratio: 10 wt%) were vacuum deposited to form a light emitting layer having a thickness of 30 nm. Then, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. Liq 1 nm (electron injection layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transport layer to produce an organic electroluminescent device as shown in Table 1. [

<Compound D>

Comparative Example  One : Synthesis of Compound [400]

The compound represented by Formula 400 (hereinafter referred to as Compound 400) was prepared according to Reaction Scheme 4 below.

[Reaction Scheme 4]

Preparation of intermediate compound [400-2]

In a 0.5 L reaction flask, 10.0 g (42.4 mmol) of the compound [400-1], 13.4 g (46.6 mmol) of the compound [119-4] and 1.0 g ) And 7.7 g (56.0 mmol) of potassium carbonate were dissolved in 210 ml of 1,4-dioxane, 42 ml of distilled water was added, and the mixture was refluxed and stirred for 24 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 8.1 g (48%) of intermediate compound [400-2].

Preparation of compound [400]

(20.3 mmol) of the compound [400-2], 9.7 g (22.4 mmol) of the compound [119-9] and 0.5 g (0.4 mmol) of tetrakis triphenylphosphinevaladium (0) And 3.7 g (26.9 mmol) of potassium carbonate are dissolved in 110 ml of 1,4-dioxane, 20 ml of distilled water is added, and the mixture is refluxed and stirred for 28 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and the solid was filtered under reduced pressure. The obtained solid was washed with methanol, distilled water and acetone, and recrystallized from tetrahydrofuran and hexane to obtain 9.7 g (76%) of compound [400] as a white solid.

Comparative Example  2 : Synthesis of Compound [500]

The compound represented by Formula 500 (hereinafter referred to as Compound 500) was prepared according to Reaction Scheme 5 below.

[Reaction Scheme 5]

Compound 500 (hereinafter referred to as Compound 500) was prepared in the same manner as in Example 1, except that Compound [119-4] was replaced by Compound [500-1].

Comparative Example  3

2-TNATA (80 nm) /? -NPD (30 nm) was prepared in the same manner as in Example 12, except that the compound 400 was used instead of the compound represented by the formula an organic electroluminescent device having a structure of Compound 400 + Compound D (30 nm) / Alq3 (30 nm) / Liq (1 nm) / Al (100 nm)

Comparative Example  4

2-TNATA (80 nm) /? -NPD (30 nm) was prepared in the same manner as in Example 12, except that Compound 500 was used instead of the compound represented by Formula nm) / Compound 500 + Compound D (30 nm) / Alq3 (30 nm) / Liq (1 nm) / Al (100 nm).

Comparative Example  5

2-TNATA (80 nm) /? -NPD (80 nm) was obtained in the same manner as in Example 12, except that the following compound E was used instead of the compound represented by the formula (1) 30 nm) / Compound E + Compound D (30 nm) / Alq3 (30 nm) / Liq (1 nm) / Al (100 nm).

(E)

Comparative Example  6

A compound represented by the following formula (F) is used as a phosphorescent green host, and a compound represented by the following formula (D) is used as a phosphorescent green dopant, and 2-TNATA (4,4'4 " ) -N-phenylamino) -triphenylamine was used as a hole injection layer material and α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine) , An organic electroluminescent device having the following structure was fabricated: ITO / 2-TNATA (80 nm) /? -NPD (30 nm) / compound F + compound D (30 nm) / Alq3 (1 nm) / Al (100 nm).

The anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TNATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. The compound represented by the formula (F) and the compound represented by the formula (D) (doping ratio: 10%) were vacuum deposited on the hole transporting layer to form a light emitting layer with a thickness of 30 nm. Then, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. Liq 1 nm (electron injection layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transport layer to produce an organic electroluminescent device as shown in Table 1. [

<Formula F>

Evaluation example  1: Evaluation of luminescence characteristics

Each of the samples of the organic electroluminescence device manufactured in Example 12-21 and Comparative Example 3-6 was evaluated using the Keithley source meter "2400" KONIKA MINOLTA "CS-2000" The results are shown in Table 1 below. The samples showed green emission peak values in the range of 513 nm to 515 nm.

Sample No. Phosphorescent green host Phosphorescent green dopant Voltage
OP. V Luminance
[cd / m ² ] efficiency
[cd / A] Emission peak
[nm] Comparative Example 3 Compound E Compound D 5.12 4759 47.59 514 Comparative Example 4 Compound F Compound D 4.89 4652 46.52 513 Comparative Example 5 Compound 400 Compound D 5.10 4498 43.11 510 Comparative Example 6 Compound 500 Compound D 4.82 4907 47.72 515 Example 11 Compound 119 Compound D 4.54 5214 52.14 513 Example 12 Compound 132 Compound D 4.65 5067 50.67 513 Example 13 Compound 163 Compound D 4.44 5128 51.28 513 Example 14 Compound 175 Compound D 4.21 5109 51.09 514 Example 15 Compound 186 Compound D 4.16 5008 50.08 515 Example 16 Compound 216 Compound D 4.79 5138 51.38 514 Example 17 Compound 235 Compound D 4.32 5205 52.05 515 Example 18 Compound 269 Compound D 4.08 5198 51.98 513 Example 19 Compound 272 Compound D 4.74 5198 51.98 513 Example 20 Compound 299 Compound D 4.01 5043 50.43 515

As shown in Table 1, the organic electroluminescent devices of Examples 11-20 showed improved luminescent characteristics as compared with the organic electroluminescent devices of Comparative Examples 3-6.

Evaluation example  2: Evaluation of life characteristics

For each sample of the organic electroluminescent device fabricated in Examples 11-20 and Comparative Examples 3-6, the time required for the lifetime to reach 97% on the basis of 3000 nits was measured using an LTS-1004AC life measuring device manufactured by ENC technology And the results are shown in Table 2 below.

Sample No. Phosphorescent green host
No. Phosphorescent green dopant
No. life span
Time (Hours) Comparative Example 3 Compound E Compound D 42 Comparative Example 4 Compound F Compound D 38 Comparative Example 5 Compound 400 Compound D 39 Comparative Example 6 Compound 500 Compound D 53 Example 11 Compound 119 Compound D 84 Example 12 Compound 132 Compound D 67 Example 13 Compound 163 Compound D 85 Example 14 Compound 175 Compound D 89 Example 15 Compound 186 Compound D 68 Example 16 Compound 216 Compound D 62 Example 17 Compound 235 Compound D 86 Example 18 Compound 269 Compound D 89 Example 19 Compound 272 Compound D 66 Example 20 Compound 299 Compound D 65

As shown in Table 2, the organic electroluminescent devices of Examples 11-20 showed improved lifetime characteristics as compared with the organic electroluminescent devices of Comparative Examples 3-6.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (15)

1. An organic electroluminescent device compound represented by the following formula (1): < EMI ID =
&Lt; Formula 1 &gt;

In this formula,
X is C (R15) (R16), C = O, O, S, N (R17), Si (CH 3) 2, SO 2, Se, substituted coupled to spiro structure or unsubstituted C6-C50 aryl A substituted or unsubstituted C5-C50 cycloalkyl group bonded through a spiro structure, and when the aryl group and the cycloalkyl group have two or more substituents, the two or more substituents are fused to form a polycyclic aliphatic or aromatic fused ring &Lt; / RTI &gt;
R1 is a phenyl group,
R2, R15, R16 and R17 are each independently selected from the group consisting of hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7- Substituted or unsubstituted C6-C50 aryl group, substituted or unsubstituted C3-C50 heteroaryl group, substituted or unsubstituted C4-C50 hetero arylalkyl group, substituted or unsubstituted C1-C50 alkyl group, An alkylamino group, a substituted or unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;
R15 and R16 may be fused together to form a polycyclic aliphatic or aromatic fused ring;
Het is a substituted or unsubstituted triazine group;
L1 and L2 are each independently a single bond, a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C7-C50 arylalkylene group, a substituted or unsubstituted C6-C50 cycloalkylene group, A substituted or unsubstituted C1-C50 alkenyl group, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C3-C50 heteroarylene group, a substituted or unsubstituted C4-C50 heteroarylalkylene group, C6-C50 arylimino group, a substituted or unsubstituted C7-C50 arylalkylimino group, or a substituted or unsubstituted C7-C50 arylalkoxyimino group.
The method according to claim 1,
Wherein the compound represented by Formula 1 is any one of compounds represented by the following Formulas 2 to 4
Compound for Organic Electroluminescent Device:
[Chemical Formula 2] &lt; EMI ID = [Chemical Formula 4]

In this formula,
A is nitrogen;
R3 and R4 are each independently selected from the group consisting of hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7-C50 arylalkyl group, a substituted or unsubstituted C4- A substituted or unsubstituted C1-C50 alkylamino group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, Or an unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;
X, R 1, R 2, L 1 and L 2 are as defined in the above formula (1).
The method according to claim 1,
Wherein the compound represented by Formula 1 is any one of compounds represented by Chemical Formulas 5 to 8
Compound for Organic Electroluminescent Device:
[Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8]

In this formula,
A is nitrogen;
R1 is a phenyl group,
R2 to R4 each independently represent hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7-C50 arylalkyl group, a substituted or unsubstituted C4- A substituted or unsubstituted C1-C50 alkylamino group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, Or an unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;
X is as defined in the above formula (1).
The method according to claim 1,
Wherein the compound represented by Formula 1 is any one of compounds represented by the following Formulas 21 to 25
Compound for Organic Electroluminescent Device:
[Chemical Formula 21] (23)

[Chemical Formula 24]

A is nitrogen;
R1 is a phenyl group,
R2, R3, R4 and R11 are each independently selected from the group consisting of hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7- Substituted or unsubstituted C6-C50 aryl group, substituted or unsubstituted C3-C50 heteroaryl group, substituted or unsubstituted C4-C50 hetero arylalkyl group, substituted or unsubstituted C1-C50 alkyl group, An alkylamino group, a substituted or unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;
L1 is as defined in the above formula (1).
The method according to claim 1,
R2, R15, R16 and R17 are each independently hydrogen (H); Deuterium (D); halogen;
C20 alkyl group, C3-C50 cycloalkyl group, C2-C50 alkenyl group, C3-C50 cycloalkenyl group, C2-C50 alkynyl group, C5-C50 cycloalkynyl group, cyano group, C1-C20 A substituted or unsubstituted heteroaryl group substituted with at least one group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group of C6-C60, and an arylalkyl group of C7-C60;
C20 alkyl group, C3-C50 cycloalkyl group, C2-C50 alkenyl group, C3-C50 cycloalkenyl group, C2-C50 alkynyl group, C5-C50 cycloalkynyl group, cyano group, C1-C20 An aryl group of C6-C60, an arylalkyl group of C7-C60, or a heteroarylalkyl group which is unsubstituted or substituted with at least one group selected from the group consisting of C7-
Wherein said heteroaryl group and said heteroarylalkyl group each independently comprise at least one heteroatom selected from heteroatom B, N, O, S, P (= O), Si and P
Compound for organic electroluminescence device.
The method according to claim 1,
Each of R2, R15, R16 and R17 is independently hydrogen, a phenyl group, a biphenyl group, a naphthyl group, a carbazole group or a pyridine group,
The L1 and L2 are each independently a single bond, a phenylene group, a biphenylene group, a naphthylene group, a carbazole group or a pyridine group
Compound for organic electroluminescence device.
The method according to claim 1,
Wherein the compound represented by Formula 1 is any one of compounds represented by Chemical Formulas 101 to 124, 126, 131 to 154, 156, 163-172, 194, 199, 201, 203, 206 to 208, and 233 to 238
Compound for organic electroluminescence device.

The organic electroluminescent device according to any one of claims 1 to 7, wherein the organic electroluminescent device comprises a structure in which a first electrode, one or more organic material layers and a second electrode are laminated, Light emitting element.
9. The method of claim 8,
Wherein the organic layer includes a light emitting layer, and the light emitting layer comprises one or more compounds for the organic electroluminescence device
Organic electroluminescent device.
10. The method of claim 9,
The compound for an organic electroluminescent device is included in a phosphorescent host, a fluorescent host, or a fluorescent dopant in the light emitting layer
Organic electroluminescent device.
9. The method of claim 8,
Wherein the organic material layer includes at least one selected from the group consisting of a hole transporting layer, a hole injecting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer and an electron blocking layer
Organic electroluminescent device.
12. The method of claim 11,
Wherein the hole transport layer, the hole injection layer, the hole blocking layer, the electron transport layer, the electron injection layer, or the electron blocking layer comprises at least one compound for the organic electroluminescence device
Organic electroluminescent device.
An electronic device comprising the organic electroluminescent device according to claim 8.
14. The method of claim 13,
The electronic device includes: an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O- ), An organic optical detector, an organic photoreceptor, an organic field-quench device (O-FQD), a luminescent electrochemical cell (LEC), an organic laser diode (O-
Electronics. The method according to claim 1,
Wherein the compound represented by Formula 1 is any one of compounds represented by the following Formulas 31 to 35
Compound for Organic Electroluminescent Device:
(31) (32)

[Chemical Formula 33] (35)

A is nitrogen;
R12 is hydrogen,
R2 to R4, R7, R11 and R13 each independently represent hydrogen (H), deuterium (D), halogen, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C7- A substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C50 heteroaryl group, a substituted or unsubstituted C4-C50 heteroarylalkyl group, a substituted or unsubstituted C1-C50 cycloalkyl group, a substituted or unsubstituted C6- A substituted or unsubstituted C7-C50 arylamino group, a substituted or unsubstituted C7-C50 arylalkylamino group, or a substituted or unsubstituted C7-C50 arylalkoxyamino group;
L1 is as defined in the above formula (1).

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