KR101764911B1 - Organic electroluminescent compound, ink composition, organic electroluminescent device and electric apparatus - Google Patents

Abstract

상기 식에서, Y, W, R¹ 및 R²은 전술하여 정의된 바와 같다.There is provided an organic light-emitting compound represented by the following formula (1).
≪ Formula 1 >

Wherein Y, W, R < ¹ > and R < ² > are as defined above.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound, an ink composition, an organic light emitting device, and an electronic device.

An organic light-emitting compound, an ink composition, an organic light-emitting device 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 light emitting device using such a principle may be generally composed 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.

As materials used in organic light emitting devices, pure organic materials or complexes in which an organic material and a metal form a complex are mostly used, and they are classified into a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, . 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 novel organic electroluminescent compounds having appropriate energy levels, electrochemical stability, and thermal stability.

Another embodiment of the present invention provides an ink composition comprising the organic luminescent compound.

Another embodiment of the present invention provides an organic light emitting device comprising the organic light emitting compound.

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

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

≪ Formula 1 >

In this formula,

Y and W are, each independently, a single ^{bond, CR 4 R 5, NR 3} , O, S, C = O, SO 2, S = O, PR 6 R 7 R 8, P (= O) R 9 or SiR ¹⁰ R ¹¹ , provided that W is not a single bond when Y is a single bond and Y is not a single bond when W is a single bond;

R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R 12 are each independently hydrogen; A substituted or unsubstituted C6 to C60 aryl group linked by - (L) _n -; A substituted or unsubstituted C3 to C60 arylalkyl group linked by - (L) _n -; A substituted or unsubstituted C3-C60 heteroaryl group linked by - (L) _n -; A substituted or unsubstituted C3-C60 heteroarylalkyl group linked by - (L) _n -; A substituted or unsubstituted C1-C20 alkylamino group linked by - (L) _n -; A substituted or unsubstituted C6 to C60 arylamino group connected by - (L) _n -; A substituted or unsubstituted C7 - C60 arylalkylamino group connected by - (L) _n -; - a substituted or unsubstituted C7-C60 arylalkoxyamino group connected by - (L) _n- ,

L is a substituted or unsubstituted C6-C60 arylene group; A substituted or unsubstituted C3 to C60 arylalkylene group; A substituted or unsubstituted C3 to C60 heteroarylene group; A substituted or unsubstituted C3 to C60 heteroarylalkylene group; A substituted or unsubstituted C1 to C20 divalent alkylamino group; A substituted or unsubstituted C6 to C60 divalent arylamino group; A substituted or unsubstituted C7 to C60 divalent arylalkylamino group; A substituted or unsubstituted divalent C7-C60 arylalkoxyamino group,

N is an integer of 0 to 5,

The heteroaryl group, the heteroaryl group, the heteroaryl group, the heteroaryl group, the alkylamino group, the arylamino group, the arylalkylamino group, the arylalkoxyamino group, the arylene group, the arylalkylene group, the heteroarylene group, The substituent when the above-mentioned heteroarylalkylene group, the divalent alkylamino group, the divalent arylamino group, the divalent arylalkylamino group and the divalent arylalkoxyamino group are substituted is a C1-C50 alkyl group, a C3-C50 cycloalkyl group , A C 2 to C 50 alkenyl group, a C 3 to C 50 cycloalkenyl group, a C 2 to C 50 alkynyl group, a C 3 to C 50 cycloalkynyl group, a cyano group, a C 1 to C 20 alkoxy group, C60 arylalkyl groups, and combinations thereof.

In another embodiment of the present invention, there is provided an ink composition comprising at least one of the organic luminescent compounds.

According to another embodiment of the present invention, there is provided an organic light emitting device comprising a structure in which a first electrode, at least one organic material layer and a second electrode are stacked, and the organic material layer includes at least one organic light emitting compound.

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

The organic luminescent compound can satisfactorily satisfy the conditions required for a material usable in an organic light emitting device, for example, suitable energy level, electrochemical stability, and thermal stability. can do.

Fig. 1 shows the 1H-NMR measurement results of the compound [23] prepared in the examples.
2 is a UV absorption spectrum for the compound [23] prepared in the example.
FIG. 3 is a graph showing the photoluminescence (PL) measurement of the compound [23] to be.
4 is a thermogravimetric analysis (TGA) graph for the compound [23] prepared in the Example.
5 is a graph of differential scanning calorimetry (DSC) measurement for the compound [23] prepared in the Example.
6 shows the 1H-NMR measurement results of the compound [58] prepared in the examples.

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.

Unless defined otherwise, the term "substituted" in the present specification means a C1-C50 alkyl group, a C3-C50 cycloalkyl group, a C2-C50 alkenyl group, a C3-C50 cycloalkenyl group, a C2-C50 alkynyl group , A C5-C50 cycloalkynyl group, a cyano group, a C1-C20 alkoxy group, a C6-C60 aryl group, a C7-C60 arylalkyl group, and combinations thereof.

In the present specification, the term "combination thereof" means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

"Hetero" as used herein, unless otherwise defined, means containing a heteroatom in one compound or substituent, wherein the heteroatom is selected from the group consisting of N, O, S, P, Lt; / RTI > For example, it may mean one to three heteroatoms in the one compound or substituent, and the remainder is carbon.

In one embodiment of the present invention, there is provided a novel organic luminescent compound represented by the following general formula (1).

≪ Formula 1 >

In this formula,

Y and W are, each independently, a single ^{bond, CR 4 R 5, NR 3} , O, S, C = O, SO 2, S = O, PR 6 R 7 R 8, P (= O) R 9 or SiR ¹⁰ R ¹¹ , provided that W is not a single bond when Y is a single bond and Y is not a single bond when W is a single bond;

R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R 12 are each independently hydrogen; A substituted or unsubstituted C6 to C60 aryl group linked by - (L) _n -; A substituted or unsubstituted C3 to C60 arylalkyl group linked by - (L) _n -; A substituted or unsubstituted C3-C60 heteroaryl group linked by - (L) _n -; A substituted or unsubstituted C3-C60 heteroarylalkyl group linked by - (L) _n -; A substituted or unsubstituted C1-C20 alkylamino group linked by - (L) _n -; A substituted or unsubstituted C6 to C60 arylamino group connected by - (L) _n -; A substituted or unsubstituted C7 - C60 arylalkylamino group connected by - (L) _n -; - a substituted or unsubstituted C7-C60 arylalkoxyamino group connected by - (L) _n- ,

L is a substituted or unsubstituted C6-C60 arylene group; A substituted or unsubstituted C3 to C60 arylalkylene group; A substituted or unsubstituted C3 to C60 heteroarylene group; A substituted or unsubstituted C3 to C60 heteroarylalkylene group; A substituted or unsubstituted C1 to C20 divalent alkylamino group; A substituted or unsubstituted C6 to C60 divalent arylamino group; A substituted or unsubstituted C7 to C60 divalent arylalkylamino group; A substituted or unsubstituted divalent C7-C60 arylalkoxyamino group,

N is an integer of 0 to 5,

The heteroaryl group, the heteroaryl group, the heteroaryl group, the heteroaryl group, the alkylamino group, the arylamino group, the arylalkylamino group, the arylalkoxyamino group, the arylene group, the arylalkylene group, the heteroarylene group, The substituent when the above-mentioned heteroarylalkylene group, the divalent alkylamino group, the divalent arylamino group, the divalent arylalkylamino group and the divalent arylalkoxyamino group are substituted is a C1-C50 alkyl group, a C3-C50 cycloalkyl group , A C 2 to C 50 alkenyl group, a C 3 to C 50 cycloalkenyl group, a C 2 to C 50 alkynyl group, a C 3 to C 50 cycloalkynyl group, a cyano group, a C 1 to C 20 alkoxy group, C60 arylalkyl groups, and combinations thereof.

Specifically, the organic light emitting compound may be a compound represented by the following formula (2) or (3).

(2)

(3)

In the general formulas (2) and (3)

R ¹ , R ² and R ³ are each independently hydrogen; A substituted or unsubstituted C6 to C60 aryl group linked by - (L) _n -; A substituted or unsubstituted C3 to C60 arylalkyl group linked by - (L) _n -; A substituted or unsubstituted C3-C60 heteroaryl group linked by - (L) _n -; A substituted or unsubstituted C3-C60 heteroarylalkyl group linked by - (L) _n -; A substituted or unsubstituted C1-C20 alkylamino group linked by - (L) _n -; A substituted or unsubstituted C6 to C60 arylamino group connected by - (L) _n -; A substituted or unsubstituted C7 - C60 arylalkylamino group connected by - (L) _n -; - a substituted or unsubstituted C7-C60 arylalkoxyamino group connected by - (L) _n- ,

L is a substituted or unsubstituted C6-C60 arylene group; A substituted or unsubstituted C3 to C60 arylalkylene group; A substituted or unsubstituted C3 to C60 heteroarylene group; A substituted or unsubstituted C3 to C60 heteroarylalkylene group; A substituted or unsubstituted C1 to C20 divalent alkylamino group; A substituted or unsubstituted C6 to C60 divalent arylamino group; A substituted or unsubstituted C7 to C60 divalent arylalkylamino group; A substituted or unsubstituted divalent C7-C60 arylalkoxyamino group,

N is an integer of 0 to 5, and when n is 0, - (L) _n - means a single bond,

The heteroaryl group, the heteroaryl group, the heteroaryl group, the heteroaryl group, the alkylamino group, the arylamino group, the arylalkylamino group, the arylalkoxyamino group, the arylene group, the arylalkylene group, the heteroarylene group, The substituent when the above-mentioned heteroarylalkylene group, the divalent alkylamino group, the divalent arylamino group, the divalent arylalkylamino group and the divalent arylalkoxyamino group are substituted is a C1-C50 alkyl group, a C3-C50 cycloalkyl group , A C 2 to C 50 alkenyl group, a C 3 to C 50 cycloalkenyl group, a C 2 to C 50 alkynyl group, a C 3 to C 50 cycloalkynyl group, a cyano group, a C 1 to C 20 alkoxy group, C60 arylalkyl groups, and combinations thereof.

In one embodiment, when R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 or R 12 is an arylalkyl group, a heteroaryl group or a heteroarylalkyl group, And the heteroarylalkyl group may be one in which at least one carbon has been replaced by a heteroatom B, N, O, S, P (= O), Si or P;

In another embodiment, the L is an arylalkylene group, a heteroarylene group, or a heteroarylalkylene group, and the arylalkylene group, the heteroarylene group, and the heteroarylalkylene group may have at least one carbon atom bonded to the hetero atom B, N, O , S, P (= O), Si or P.

In another embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R 12 are each independently any one of groups represented by the following structural formulas:

,

,

, 또는

이며, 각각 하나의 환속에 4개 이상 질소인 경우는 제외하며, X가 질소이면 그 옆의 X는 질소가 아니며; X is, each independently, CH, CD, CF, CCN , COCH 3, C (CH 3), CCH (CH 3) 2, _{CC (CH 3) 3, C} (CH 2) p CH 3, CCF 3, N,

,

,

, or

And each X is nitrogen, provided that X is not nitrogen;

Q is CH ₂ , C (CH ₃ ) ₂ , C ((CH ₂ ) _p CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, or S and p is an integer from 1 to 10;

이며;G is CH ₂ , C (CH ₃ ) ₂ , C = O, O, S, SO ₂ , Se or

;

L is selected from a single bond and a group represented by the following structural formula,

X in the formula representing L is the same as X defined above.

In another embodiment, R 1 and R 2 are each independently any one of groups represented by the following structural formulas,

,

,

, 또는

이며, 각각 하나의 환속에 4개 이상 질소인 경우는 제외하며, X가 질소이면 그 옆의 X는 질소가 아니고, p는 1 ~ 10까지의 정수이며;X is, each independently, CH, CD, CF, CCN , COCH 3, C (CH 3), CCH (CH 3) 2, _{CC (CH 3) 3, C} (CH 2) p CH 3, CCF 3, N,

,

,

, or

And X is nitrogen, X is not nitrogen and p is an integer of 1 to 10;

Q is CH ₂ , C (CH ₃ ) ₂ , C ((CH ₂ ) _r CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, or S and r is an integer from 1 to 10;

q is an integer from 0 to 2;

L is selected from a single bond and a group represented by the following structural formula,

X and Q in the formula representing L are the same as X and Q defined above.

For example, the organic luminescent compound may be any one of compounds 1 to 262 described in Table 1 below.

In another embodiment of the present invention, there is provided an ink composition comprising at least one of the organic luminescent compounds.

The ink composition may be a solution or suspension comprising a solvent and the solvent is selected from the group consisting of anisole, dimethyl anisole, xylene, o-xylene, m-xylene, p-xylene, toluene, But are not limited to, tetrahydrofuran, tetrahydrofuran, methylene benzoate, dioxane, terahydrofuran, methyltetrahydrofuran, tetrahydropyrane, tetralin, veratrol, chlorobenzene, N-methylpyrrolidone, And a combination thereof.

The organic compound layer can be formed by applying the ink composition and removing the solvent to form a film.

The ink composition may further comprise a pigment or a dye.

The ink composition may further comprise a phosphorescent dopant or a fluorescent dopant.

According to another embodiment of the present invention, there is provided an organic light emitting device comprising a structure in which a first electrode, at least one organic material layer and a second electrode are stacked, and the organic material layer includes at least one organic light emitting compound.

The organic light emitting compound contained in the organic material layer of the organic light emitting device is a compound represented by the general formula (1), and a detailed description thereof is as described above.

The organic material layer may be produced by a known manufacturing method of forming or laminating an organic thin film layer, or the organic material layer may be prepared by a solution process using the ink composition as described above.

In one embodiment, the organic layer may include a light emitting layer, the light emitting layer may include the organic light emitting compound, and the organic light emitting compound may be included as a phosphorescent host, a fluorescent host, a phosphorescent dopant, or a fluorescent dopant material 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 each be formed using a known material or may include one or more organic electroluminescent compounds represented by Formula 1 .

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

The organic light emitting device can be applied to various applications. For example, the electronic device to which the organic light emitting device is applied may include an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O- ), An organic photovoltaic 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 (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 )

Hereinafter, the reaction examples and the comparative examples are specifically exemplified, but the present invention is not limited to the following synthesis examples and examples. In the following reaction examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, Compound 1 is represented by the compound [1], and the intermediate compound of the above compound is represented by [1-1] or the like. In the present specification, the numbers of the compounds are represented by the numbers of the formulas shown in Table 1 above. For example, compounds designated 1 in Table 1 are designated Compound 1.

Synthetic example  1: Preparation of compound [23]

[Reaction Scheme 1]

Preparation of intermediate compound [23-2]

In a nitrogen atmosphere, 30.0 g (116.67 mmol) of 2-bromophenanthrene, 29.8 g (151.67 mmol) of compound [23-1], 4.04 g (3.50 mmol) of tetrakis (triphenylphosphine) palladium, (175.00 mmol), distilled water (80 mL) and toluene (450 mL), and the mixture was stirred at 110 DEG C for 24 hours. After completion of the reaction, 1 L of methanol was added at room temperature to solidify it. The resulting solid was filtered and refluxed with 300 mL of acetone. After cooling to room temperature, it was filtered and dried to prepare 26 g (67 wt%) of an intermediate compound [23-2] as a greenish yellow solid.

Preparation of intermediate compound [23-3]

26.0 g (78.94 mmol) of the compound [23-2], 51.7 g (197.3 mmol) of triphenylphosphine and 240 mL of 1,2-dichlorobenzene were placed in a reaction flask, and the mixture was refluxed with stirring for 12 hours. After cooling to room temperature, the pale gray solid was filtered to obtain 15.0 g (64 wt%) of the intermediate compound [23-3]

Preparation of compound [23]

(18.70 mmol) of the intermediate compound [23-3], 7.45 g (18.70 mmol) of the compound [23-4] and 171 mg (0.187 mmol) of tris (dibenzylideneacetone) dipalladium (0) , 2.69 g (28.05 mmol) of sodium tert-butoxide, 100 ml of toluene and 0.18 ml (0.374 mmol) of triethylphosphine were added and the mixture was stirred under reflux for 3 hours. The reaction mixture was cooled to room temperature, and the resulting solid was filtered off and washed with purified water and methanol. The filtered solid was recrystallized with toluene to give 8.1 g (74 wt%) of the target compound [23] as a white solid.

^{1 H NMR [400 MHz, THF} -d 8] δ 8.92 (d, 1H), 8.77 (d, 1H), 8.73 (d, 1H), 8.50 (d, 1H), 8.32 (dd, 2H), 8.18 ( (m, 4H), 7.48-7.41 (m, 3H), 7.37-7.31 (m, 2H), 7.95 (d, m, 3H)

MS / FAB (M ^< ^{+ &} gt ^; ): 584

1 is a ¹ H-NMR spectrum of the obtained compound [23].

2 is a UV absorption spectrum of the obtained compound [23].

3 is a graph showing the photoluminescence (PL) measurement of the obtained compound [23] to be.

4 is a thermogravimetric analysis (TGA) graph for the obtained compound [23].

5 is a graph of differential scanning calorimetry (DSC) measurement for the compound [23] obtained above.

Synthetic example  2: Preparation of compound [58]

[Reaction Scheme 2]

(18.70 mmol) of the intermediate compound [23-3], 7.26 g (18.70 mmol) of the compound [58-1] and 171 mg (0.20 mmol) of tris (dibenzylideneacetone) dipalladium The reaction was carried out by adding 2.69 g (28.05 mmol) of sodium tert-butoxide, 100 mL of toluene and 0.18 mL (0.374 mmol) of triethylphosphine to obtain 7.1 g (66 wt%) of the target compound [58] Respectively.

^{1 H-NMR [400 MHz,} THF-d 8] δ 9.18 (d, 1H), 9.14 (t, 1H), 8.92 (d (1H), 8.82 (s, 2H), 8.80 (d, 3H), 8.53 (m, 2H), 7.30 (d, 1H), 8.34 (d, , 1H)

MS / FAB (M ^< ^{+ &} gt ^; ): 574

6 is a ¹ H-NMR graph of the obtained compound [58].

Synthetic example  3: Preparation of compound [159]

[Reaction Scheme 3]

Preparation of intermediate compound [159-5]

159-3] was prepared in the same manner as in Synthesis Example 1, except that the compound [159-1] was used, and then 15 g (50.44 mmol) of the intermediate compound [159-3] 461 mg (0.504 mmol) of tris (dibenzylideneacetone) dipalladium, 6.30 g (65.57 mmol) of sodium tert-butoxide, 300 mL of toluene, 0.49 g mL (1.00 mmol) was added and the mixture was stirred under reflux for 4 hours. The reaction mixture was cooled to room temperature and the resulting solid was filtered off and washed with purified water and methanol. The filtered solid was dissolved in dichloromethane and filtered through silica. The filtrate was distilled under reduced pressure and dichloromethane and hexane were used to prepare 12.1 g (64 wt%) of a gray solid intermediate compound [159-5].

Preparation of intermediate compound [159-6]

To the reaction flask, 22.3 g (0.192 mol) of pyridine hydrochloride was added to 12.0 g (32.13 mmol) of the intermediate compound [159-5], and the mixture was heated and stirred at 210 to 220 ° C for 3 hours. The mixture was cooled to 80 DEG C and 300 mL of purified water was added thereto, and the solid was filtered. The obtained solid was extracted with dichloromethane, dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The concentrate was crystallized from dichloromethane and hexane and dried in vacuo. The obtained solid was dissolved in 100 mL of pyridine, and 13.6 g (48.19 mmol) of anhydrous triflic sulfonic acid was added dropwise in an ice water bath. After stirring at room temperature for 12 hours, the purified water was slowly added, and the organic layer was separated, dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. 8.1 g (51 wt%) of the intermediate compound [159-6] was prepared using dichloromethane and hexane.

Preparation of compound [159]

(12.20 mmol) of the intermediate compound [159-6], 2.04 g (12.20 mmol) of the compound [159-7], and tris (dibenzylideneacetone) di (82%) of the target compound [160] as a white solid by adding 223 mg (0.244 mmol) of palladium (0), 1.76 g (18.30 mmol) of sodium tert- butoxide, 100 mL of toluene and 0.24 mL (0.488 mmol) ).

^{1 H-NMR [400 MHz,} THF-d 8] δ 8.93 (d, 2H), 8.57 (d, 1H), 8.10 (m, 2H), 8.00 ~ 7.82 (m, 6H), 7.70 ~ 7.50 (m, 10H), 7.35-7.25 (m, 3H)

MS / FAB (M ^< ^{+ &} gt ^; ): 508

Synthetic example  4: Preparation of compound [181]

[Reaction Scheme 4]

Preparation of intermediate compound [181-1]

To the reaction flask were added 8.0 g (16.27 mmol) of the intermediate compound [159-6], 5.78 g (22.78 mmol) of bis (pinacolato) diboron, 595 mg (0.813 mmol) of Pd (dppf) Cl _2, 4.79 g mmol) were refluxed with 100 mL of 1,4-dioxane in a nitrogen atmosphere for 12 hours. The reaction solution was cooled to room temperature and the resulting solid was filtered. The solid was separated and purified by column chromatography to obtain 5.6 g (73 wt%) of the intermediate compound [181-1].

Preparation of compound [181]

(11.72 mmol) of the intermediate compound [159-6] and 5.5 g (11.72 mmol) of the intermediate compound [181-1], 270 mg (0.234 mmol) of tetrakis (triphenylphosphine) palladium, 2.43 g (17.58 mmol), and the mixture was stirred under reflux for 6 hours with 100 mL of 1,4-dioxane and 10 mL of purified water under a nitrogen stream. After completion of the reaction, the reaction solution was slowly cooled to room temperature, and then the reaction solution was filtered. The filtered solid was washed with purified water and methanol, and recrystallized from dichloromethane and methanol to obtain 7.1 g (71% by weight) of white target compound [181].

^{1 H NMR [400 MHz, THF} -d 8] δ 8.95 ~ 8.92 (m, 4H), 8.20 ~ 8.10 (m, 4H), 8.00 (m, 2H), 7.89 ~ 7.75 (m, 12H), 7.70 ~ 7.45 (m, 10H)

MS / FAB (M ^< ^{+ &} gt ^; ): 684

Synthetic example  5: Preparation of compound [219]

[Reaction Scheme 5]

Preparation of intermediate compound [219-2]

To the reaction flask were added 30.0 g (116.7 mmol) of 2-bromophenanthrene, 18.9 g (140.0 mmol) of the compound [219-1], 524 mg (2.33 mmol) of palladium (II) acetate, 24.2 g (175.1 mmol) And 2.2 mL (4.66 mmol) of trimethylbutylphosphine were added thereto, and the mixture was refluxed with stirring for 24 hours. After completion of the reaction, saturated aqueous ammonium solution was poured into the reaction solution 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 then purified by column chromatography to obtain 28.2 g (78 wt%) of intermediate compound [219-2] as a yellow solid.

Preparation of intermediate compound [219-3]

In a nitrogen atmosphere, 28.0 g (89.92 mmol) of the compound [219-2] and 600 mL of tetrahydrofuran were added to a reaction flask and stirred. To the reactor was slowly added dropwise 90.0 mL (269.7 mmol) of 3M methylmagnesium chloride and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the reaction solution was slowly poured into a saturated aqueous ammonium solution and the organic layer was separated with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to give 25.1 g (85 wt%) of yellow intermediate compound [219-3].

Preparation of intermediate compound [219-4]

In a nitrogen atmosphere, 25.0 g (76.35 mmol) of the compound [219-3] and 500 mL of dichloromethane were placed in a reaction flask and stirred. Sulfonic acid (14.9 mL, 229.0 mmol) was added to the reactor and stirred at room temperature for 12 hours. After completion of the reaction, the saturated aqueous ammonium solution was poured 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 then purified by column chromatography to obtain 19.5 g (82 wt%) of intermediate compound [219-4] as a white solid.

Preparation of compound [219]

(19.39 mmol), 7.72 g (19.39 mmol) of compound [23-4] and 177 mg (0.193 mmol) of tris (dibenzylideneacetone) dipalladium (0) in the same manner as in Synthesis Example 1 ), Sodium tartrate butoxide (2.80 g, 29.08 mmol), toluene (100 mL) and triethylphosphine (0.19 mL, 0.39 mmol) were added and reacted to prepare 8.0 g (66 wt%) of the target compound [220] as a white solid.

^{1 H NMR [400 MHz, THF} -d 8] δ 8.95 (d, 1H), 8.55 ~ 8.50 (m, 2H), 8.15 (d, 1H), 7.95 ~ 7.70 (m, 8H), 7.58 ~ 7.40 (m , 7H), 7.30-7.21 (m, 2H), 7.05-7.00 (m, 3H), 6.75-6.55

MS / FAB (M ^< ^{+ &} gt ^; ): 626

Synthetic example  6: Preparation of compound [238]

[Reaction Scheme 6]

Preparation of intermediate compound [238-2]

30.0 g (154.4 mmol) of 1-hydroxypentanthrene was added to the reaction flask, and the mixture was stirred in a nitrogen atmosphere with 500 mL of dimethylformamide. 11.1 g (231.6 mmol) of 50% NaH was slowly added at room temperature. After stirring for 10 minutes, 26.1 g (185.2 mmol) of 2-fluoronitrobenzene was added dropwise. After completion of dropwise addition, the reaction solution was poured into purified water after stirring at room temperature for 6 hours. The resulting solid was filtered. The solid was dissolved in 500 mL of dichloromethane, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from methanol to obtain 28.1 g (58 wt%) of yellow intermediate compound [238-2].

Preparation of intermediate compound [238-3]

28.0 g (88.80 mmol) of the intermediate compound [238-2], 58.2 g (222.0 mmol) of triphenylphosphine, 1,2-dichlorobenzene 21.0 g (83%) of intermediate compound [238-3] was prepared.

Preparation of compound [238]

(18.70 mmol) of intermediate compound [238-3], 7.45 g (18.70 mmol) of compound [23-4] and 171 mg (0.187 mmol) of tris (dibenzylideneacetone) dipalladium (0) were obtained in the same manner as in Synthesis Example 1. [ (74 wt%) of the desired compound [238] as a white solid was prepared by adding 2.69 g (28.05 mmol) of sodium tert-butoxide, 100 mL of toluene and 0.18 mL (0.374 mmol) of triethylphosphine.

^{1 H NMR [400 MHz, THF} -d 8] δ 8.92 (d, 1H), 8.56 (d, 1H), 8.45 (d, 1H), 8.10 (d, 1H), 7.94 ~ 7.60 (m, 8H), 7.55-7.45 (m, 7H), 7.30 (m, 2H), 7.04-6.69 (m, 7H)

MS / FAB (M ^< ^{+ &} gt ^; ): 600

Synthetic example  7-10

The compound [25], the compound [115], the compound [128] and the compound [201] were synthesized using a suitable compound only in the above Synthesis Example 1 substituting only the substituent.

Comparative Example  One

Wherein the compound represented by the following formula (a) is used as a phosphorescent green host and the compound represented by the following formula (c) is used as a phosphorescent green dopant, and 2-TNATA (4,4 ' (N, N'-di (naphthylene-1-yl) -N, N'-diphenylbenzidine) was used as a hole transport layer material (30 nm) / Alq ₃ (30 nm) / Liq (30 nm) / a-NPD (30 nm) / ITO / 2-TNATA (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. A compound represented by the formula (a) and a compound represented by the formula (c) (doping ratio: 10 wt%) were vacuum deposited on the hole transport layer to form a light emitting layer with a thickness of 30 nm. Then, an Alq ₃ 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 injecting layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to form an organic light emitting device as shown in Table 1. This is referred to as Comparative Sample 1.

Comparative Example  2

Wherein the compound represented by the following formula (b) is used as a phosphorescent green host and the compound represented by the following formula (c) is used as a phosphorescent green dopant, and 2-TNATA (4,4 ' (N, N'-di (naphthylene-1-yl) -N, N'-diphenylbenzidine) was used as a hole transport layer material (30 nm) / Alq ₃ (30 nm) / Liq (30 nm) / a-NPD (30 nm) (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. A compound represented by the formula (b) and a compound represented by the formula (c) (doping ratio: 10 wt%) were vacuum-deposited on the hole transport layer to form a 30 nm thick light emitting layer. Then, an Alq ₃ 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 injecting layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to form an organic light emitting device as shown in Table 1. This is referred to as Comparative Sample 2.

(Formula a) < Formula b >

 <Formula c>

Example  1 to 10

Except that phosphorescent green host (a) was used instead of phosphorescent green host (23), compound 23, 25, 58, 115, 128, 159, 181, 201, 219 and 238 synthesized in Synthesis Example 1-10 (30 nm) / Compound 23, 25, 58, 115, 128, 159, 181, 201, 219, and 238 + were prepared in the same manner as in Comparative Example 1, (30 nm) / Alq ₃ (30 nm) / Liq (1 nm) / Al (100 nm). These are referred to as Samples 1 to 10, respectively.

Evaluation example  1: Evaluation of luminescence characteristics of Comparative Sample 1 and Samples 1 to 10

Comparative Example 1 and Samples 1 to 10 were evaluated for light emission luminance, light emission efficiency and emission peak using Keithley source meter "2400" and KONIKA MINOLTA "CS-2000", respectively, and the results are shown in Table 2 below. The samples showed green emission peak values in the range of 513-515 nm.

Sample No. Phosphorescent green host
No. Phosphorescent green dopant
No. Voltage
OP. V Luminance
[cd / m ² ] efficiency
[cd / A] Emission peak
[nm] Comparative Sample 1 a c 5.12 4759 47.59 514 Comparative Sample 2 b c 4.89 4652 46.52 513 One 23 c 4.58 5099 50.99 515 2 25 c 4.25 4941 49.41 514 3 58 c 4.64 5246 52.46 513 4 115 c 4.34 4985 49.85 513 5 128 c 4.13 5097 50.97 514 6 159 c 4.54 5094 50.94 515 7 181 c 4.63 4941 49.41 515 8 201 c 4.75 5077 50.77 514 9 219 c 4.35 4952 49.52 515 10 238 c 4.62 5204 52.04 515

As shown in Table 2, Samples 1 to 10 exhibited improved luminescence characteristics as compared with Comparative Samples 1 and 2.

Evaluation example  2: Evaluation of life characteristics of Comparative Sample 1 and Samples 1 to 10

The comparative sample 1 and samples 1 to 10 were measured for time to reach 97% of life on the basis of 300 nits using an LTS-1004AC life measuring device manufactured by ENC technology, and the results are shown in Table 3 below .

Sample No. Phosphorescent green host
No. Phosphorescent green dopant
No. life span
Time [Hours] Comparative Sample 1 a c 45 Comparative Sample 2 b c 53 One 23 c 64 2 25 c 67 3 58 c 88 4 115 c 71 5 128 c 73 6 159 c 73 7 181 c 74 8 201 c 65 9 219 c 66 10 238 c 65

As shown in Table 3, Samples 1 to 10 exhibited improved life characteristics compared to Comparative Samples 1 and 2.

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 (20)

An organic electroluminescent compound represented by the following formula (58), (128) or (159).

delete delete delete delete delete delete The method according to claim 1,
The organic luminescent compound is used as a material of an organic film for an organic light emitting device
Organic luminescent compound.
An ink composition comprising at least one organic electroluminescent compound according to any one of claims 1 to 8.
10. The method of claim 9,
The ink composition may be a solution or suspension further comprising a solvent,
Ink composition.
10. The method of claim 9,
Further comprising a pigment or dye
Ink composition.
10. The method of claim 9,
Further comprising a phosphorescent dopant or a fluorescent dopant
Ink composition.
Wherein the first electrode, the organic layer including one or more organic layers, and the second electrode are stacked, and the organic layer includes at least one organic electroluminescent compound according to claim 1.
14. The method of claim 13,
Wherein the organic layer includes a light-emitting layer, and the light-emitting layer comprises at least one organic light-emitting compound according to claim 1
Organic light emitting device.
15. The method of claim 14,
The organic luminescent compound may be included in the luminescent layer as a phosphorescent host, a fluorescent host, a phosphorescent dopant, or a fluorescent dopant material
Organic light emitting device.
14. The method of claim 13,
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 light emitting device.
17. The method of claim 16,
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 organic electroluminescent compound according to claim 1
Organic light emitting device.
14. The method of claim 13,
Wherein the organic material layer is formed by applying an ink composition containing at least one organic electroluminescent compound according to claim 1 by a solution process,
Organic light emitting device.
An electronic device comprising the organic light-emitting device according to claim 13.
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