KR20150041506A - Compound, organic optoelectric device and display device - Google Patents

Abstract

The present invention relates to a compound, an organic optoelectronic device, and a display device comprising the organic optoelectronic device. According to the present invention a compound represented by the following Chemical Formula 1. [Chemical Formula 1] In the above Chemical Formula 1, R^1 to R^6, X^1, X^2, M, n, and m are as defined in the detailed description.

Description

TECHNICAL FIELD [0001] The present invention relates to a compound, an organic optoelectronic device including the same, and a display device.

Organic optoelectronic devices, and display devices.

Organic optoelectronic devices are devices that can switch between electrical and optical energy.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle. One is an optoelectronic device in which an exciton formed by light energy is separated into an electron and a hole, the electron and hole are transferred to different electrodes to generate electric energy, and the other is a voltage / Emitting device that generates light energy from energy.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, and organic photo conductor drums.

In recent years, organic light emitting diodes (OLEDs) have attracted considerable attention due to the demand for flat panel display devices. The organic light emitting diode is a device for converting electrical energy into light by applying an electric current to the organic light emitting material, and usually has an organic layer inserted between an anode and a cathode. The organic layer may include a light emitting layer and an optional auxiliary layer. The auxiliary layer may include, for example, a hole injecting layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, And a hole blocking layer.

The performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and the organic layer is highly affected by the organic material contained in the organic layer.

In particular, in order for the organic light emitting device to be applied to a large-sized flat panel display device, it is necessary to develop an organic material capable of increasing the mobility of holes and electrons and increasing the electrochemical stability.

And a compound capable of providing an organic optoelectronic device having characteristics such as high efficiency, long life, and thermal stability.

An organic light emitting device including the compound, and a display device including the organic light emitting device.

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

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted silyl group,

Wherein one of R ¹ to R ³ is a substituted or unsubstituted C6 to C30 aryl group,

Any one of R ⁴ to R ⁶ is a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted silyl group,

X ¹ and X ² are each independently O, S, SO, SO ₂ , POR ⁷ , NR ⁸ , CR ⁹ R ¹⁰ , or SiR ¹¹ R ¹² ,

Wherein R ⁷ to R ¹² are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 hetero An arylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C30 aryloxycar A substituted or unsubstituted C1 to C30 sulfamoylamino group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C2 to C30 alkynyl group, A substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C1 to C20 acyloxy group, a substituted or unsubstituted C1 to C20 acylamino group, a substituted or unsubstituted C1 to C20 acyl group, A substituted or unsubstituted C1 to C30 alkylthiol group, a substituted or unsubstituted C1 to C30 heterocyclothiol group, a substituted or unsubstituted C6 to C30 arylthiol group, a substituted or unsubstituted C1 to C30 arylthiol group, A halogen atom, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a perorenyl group or a substituted or unsubstituted C1 to C30 heteroarylthiol group Or

R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are fused to form a ring,

M is Ir, Os, Pt, Pb, Re, Ru, or Pd,

n And m are each independently any one of integers 1 and 2, and n + m is an integer of 3.

According to another embodiment of the present invention, there is provided an organic electroluminescence device comprising: an anode and a cathode facing each other; and at least one organic layer positioned between the anode and the cathode, wherein the organic layer comprises a compound according to an embodiment of the present invention Organic photovoltaic devices.

According to another embodiment of the present invention, there is provided a display device including an organic optoelectronic device, which is an embodiment of the present invention described above.

The organic optoelectronic device including the above compound has excellent electrochemical and thermal stability, has excellent lifetime characteristics, and can have a high luminous efficiency even at a low driving voltage. The compound for organic optoelectronic devices may also be suitable for a deposition process or a solution process.

1 and 2 are cross-sectional views illustrating various embodiments of an organic light emitting device that can be manufactured using the compound according to one embodiment of the present invention.

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

As used herein, unless otherwise defined, at least one of the substituents or at least one hydrogen in the compound is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, C1 to C10 alkyl groups such as a C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, A trifluoroalkyl group or a cyano group.

A substituted or unsubstituted C1 to C20 amine group, a nitro group, a substituted or unsubstituted C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C10 alkylsulfinyl group, A C1 to C10 trifluoroalkyl group such as a C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group or a trifluoromethyl group, or a cyano group may be fused together to form a ring .

Means one to three heteroatoms selected from the group consisting of N, O, S and P in one functional group, and the remainder is carbon, unless otherwise defined.

As used herein, the term "alkyl group" means an aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an alkyl group of C1 to C20. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are included in the alkyl chain and include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec- Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And the like.

The term "aryl group" means a substituent in which all the elements of the cyclic substituent have p-orbital, and these p-orbital forms conjugation, and monocyclic or fused ring polycyclic , Rings that divide adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means that the aryl group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

More specifically, the substituted or unsubstituted aryl group and / or the substituted or unsubstituted heteroaryl group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, A substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group , A substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrazinyl group, A thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, A substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, A substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted benzothiazyl group, A substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, wherein the substituted or unsubstituted dithiocarbamoyl group is a substituted phenoxyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, But is not limited thereto.

In the present specification, the hole property means a property of facilitating the injection into the light emitting layer and the movement in the light emitting layer of the hole formed in the anode due to conduction characteristics along the HOMO level. More specifically, it may be similar to the characteristic of pushing electrons.

Further, the electron characteristic means a property of facilitating the injection of electrons formed in the anode into the luminescent layer and the movement in the luminescent layer due to conduction characteristics along the LUMO level. More specifically, it may be similar to the characteristic of attracting electrons.

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

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted silyl group,

Wherein one of R ¹ to R ³ is a substituted or unsubstituted C6 to C30 aryl group,

Any one of R ⁴ to R ⁶ is a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted silyl group,

X ¹ and X ² are each independently O, S, SO, SO ₂ , POR ⁷ , NR ⁸ , CR ⁹ R ¹⁰ , or SiR ¹¹ R ¹² ,

Wherein R ⁷ to R ¹² are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 hetero An arylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C30 aryloxycar A substituted or unsubstituted C1 to C30 sulfamoylamino group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C2 to C30 alkynyl group, A substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C1 to C20 acyloxy group, a substituted or unsubstituted C1 to C20 acylamino group, a substituted or unsubstituted C1 to C20 acyl group, A substituted or unsubstituted C1 to C30 alkylthiol group, a substituted or unsubstituted C1 to C30 heterocyclothiol group, a substituted or unsubstituted C6 to C30 arylthiol group, a substituted or unsubstituted C1 to C30 arylthiol group, A halogen atom, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a perorenyl group or a substituted or unsubstituted C1 to C30 heteroarylthiol group Or

R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are fused to form a ring,

M is Ir, Os, Pt, Pb, Re, Ru, or Pd,

n And m are each independently any one of integers 1 and 2, and n + m is an integer of 3.

In this case, the compound represented by the formula (1) has excellent heat stability and lifetime characteristics and can have a high luminous efficiency even at a low driving voltage.

Specifically, the compounds according to one embodiment of the present invention introduce substituents at R ¹ to R ³ and R ⁴ to R ⁶ of at least one ligand to reduce the most problematic triplet-triplet extinction phenomenon in OLEDs In addition, by increasing the affinity with the host and suppressing the triplet-triplet extinction phenomenon by the aggregation, the luminous efficiency and luminance characteristics can be improved as compared with the case where the conventional phenylpyridine-based iridium compound is used have.

In addition, when X ¹ or X ² is bridged, a compound represented by the above formula (1) may show a blue shift as compared with a compound in which X ¹ or X ² is not bridged, The compound according to one embodiment of the present invention can efficiently emit light ranging from blue to green.

As a specific example, any one of R ¹ to R ³ may be a substituted or unsubstituted C6 to C10 aryl group, more specifically, a substituted or unsubstituted phenyl group.

Any one of R ⁴ to R ⁶ may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted silyl group, Or a substituted or unsubstituted phenyl group, more specifically, an unsubstituted methyl group, an unsubstituted ethyl group, an isopropyl group, a t-butyl group, a trimethylsilyl group, or an unsubstituted phenyl group.

When R ¹ to R ⁶ are as described above, it is possible to produce an organic optoelectronic device having excellent heat stability and lifetime characteristics and high luminous efficiency even at a low driving voltage.

In particular, when any one of R ¹ to R ³ is a phenyl group, the color purity of the green light emission is not changed, and the effect of increasing the total volume of the molecules is minimized, so that the intermolecular interaction is minimized, so that a light emitting device with high efficiency and long life can be realized.

X ¹ and X ² are each independently O, S, POR ⁷ , NR ⁸ , CR ⁹ R ¹⁰ , or SiR ¹¹ R ¹² , wherein R ⁷ to R ¹² are each independently a C 1 to C 4 alkyl group .

For example, in Formula 1, any one of R ¹ to R ³ is a substituted or unsubstituted phenyl group, and any one of R ⁴ to R ⁶ is an unsubstituted methyl group, an unsubstituted ethyl group, an isopropyl group, a t-butyl A trimethylsilyl group or an unsubstituted phenyl group; and X ¹ and X ² are each independently CR ⁹ R ¹⁰ , wherein R ⁹ and R ¹⁰ may each independently be a C1 to C4 alkyl group.

The specific examples, R ¹ is an unsubstituted phenyl group, R ⁵ is an unsubstituted methyl group, a unsubstituted ethyl group, an isopropyl group, a t- butyl group, or a trimethylsilyl group ring, R ⁹ and R ¹⁰ are each independently a ring Methyl group. However, the present invention is not limited thereto.

In this case, the compound can realize excellent heat stability, life characteristics, and luminous efficiency.

Specific examples of the compound according to one embodiment of the present invention include, but are not limited to, any of the compounds listed in Group I below.

[Group I]

Hereinafter, an organic optoelectronic device to which the above-described compound is applied will be described.

In another embodiment of the present invention, there is provided an organic optoelectronic device including an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, wherein the organic layer comprises the above-described compound .

The organic layer includes a light emitting layer, and the light emitting layer may include the compound.

The compound is used in an organic layer to improve lifetime characteristics, efficiency characteristics, electrochemical stability and thermal stability of an organic optoelectronic device, and can lower a driving voltage.

More specifically, the organic optoelectronic device may be an organic light emitting device.

1 and 2 are sectional views of an organic light emitting device including a compound according to an embodiment of the present invention.

Referring to FIGS. 1 and 2, organic light emitting devices 100 and 200 according to an embodiment of the present invention include an anode 120, a cathode 110, and at least one organic layer 105).

The anode 120 includes a cathode material. As the anode material, a material having a large work function is preferably used to facilitate injection of holes into the organic thin film layer. Specific examples of the positive electrode material include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or alloys thereof and zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide ), And combinations of metals and oxides such as ZnO and Al or SnO ₂ and Sb, and poly (3-methylthiophene), poly (3,4- (ethylene- 2-dioxythiophene (PEDT), polypyrrole, and polyaniline, but the present invention is not limited thereto. Preferably, a transparent electrode including ITO (indium tin oxide) may be used as the anode.

The cathode 110 includes a cathode material, and the anode material is preferably a material having a small work function to facilitate electron injection into the organic thin film layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium and the like, , LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca. However, the present invention is not limited thereto. Preferably, a metal electrode such as aluminum or the like may be used for the negative electrode.

1 illustrates an organic light emitting device 100 in which only a light emitting layer 130 is present as an organic layer 105. The organic layer 105 may exist only in the light emitting layer 130. FIG.

2 shows a two-layer type organic light emitting diode 200 having a light emitting layer 230 including an electron transporting layer and a hole transporting layer 140 as an organic layer 105. As shown in FIG. 2, , And the organic layer 105 may be a two-layer type including a light emitting layer 230 and a hole transporting layer 140. In this case, the light emitting layer 230 functions as an electron transporting layer, and the hole transporting layer 140 functions to improve the bonding property with a transparent electrode such as ITO and the hole transporting property. 1 and 2, the organic layer 105 may further include an electron injecting layer, an auxiliary electron transporting layer, an electron transporting layer, an electron transporting layer, an auxiliary electron transporting layer, and an electron injecting layer, though not shown.

1 and 2, the light emitting layers 130 and 230, the hole transporting layer 140 and the electron injecting layer, the auxiliary electron transporting layer, the electron transporting layer, the major transporting layer, and the auxiliary (not shown) A hole transporting layer, a hole transporting layer, a hole injecting layer, and combinations thereof, includes a compound for the organic optoelectronic device.

In particular, the compound for the organic optoelectronic device can be used for the light emitting layers 130 and 230, and can be used as a green phosphorescent dopant material in the light emitting layer.

The organic light emitting device described above may be formed by a dry film forming method such as evaporation, sputtering, plasma plating, and ion plating after an anode is formed on a substrate; Or a wet film formation method such as spin coating, dipping or flow coating, and then forming a cathode on the organic thin film layer.

In another embodiment of the present invention, there is provided a display device including the organic optoelectronic device.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

(Preparation of compound)

Manufacturing example  1: D- 1 of  Produce

[Reaction Scheme 1]

compound- 1 of  Produce

To a round bottom flask was added 35.2 g (177.7 mmol) of biphenyl-3-yl boronic acid, 30 g (161.6 mmol) of methyl 2-chloro-5-methylnicotinate in the presence of tetrakis (triphenylphosphine) palladium [ ₃ ) ₄ ] 5.6 g (4.84 mmol) of potassium carbonate and 44.68 g (323 mmol) of potassium carbonate were added to 600 mL of THF and 300 mL of distilled water and the mixture was refluxed for 24 hours. When the reaction is complete, cool to room temperature and separate THF and distilled water. Add 1200 mL of methanol to THF and crystallize. The resulting solid was filtered and washed with water and methanol. The solids were dried in a vacuum oven to obtain 35 g (yield: 71%) of Compound-1.

compound- 2 of  Produce

Add 35 g (115 mmol) of compound-1 to a round bottom flask and dissolve in 700 mL of anhydrous THF. Add 307 mL of methylmagnesium bromide solution to the flask at 0 ° C. After completion of the reaction, the ammonium chloride is dissolved in 150 ml of water and quenched. The organic layer and the water layer are separated, and then all of the solvent is removed. 32 g (yield: 91%) of Compound-2 was obtained by column chromatography.

compound- 3 of  Produce

32 g (105 mmol) of Compound-2 was dissolved in the MC solution in a round bottom flask under a nitrogen stream, and 13.2 mL (105 mmol) of boron trifluoride diethylsulfate was added dropwise. After stirring for one day, water is added to dissolve the sodium bicarbonate. After completion of the reaction, the organic layer was separated, and then all of the solvent was removed. Then, 25 g (yield: 83%) of Compound-3 was obtained using hexane.

compound- 4 of  Produce

11.9 g (41.8 mmol) of Compound-3, 5 g (16.7 mmol) of iridium chloride, 90 mL of 2-ethoxyethanol and 30 mL of distilled water were added to a round bottom flask, and the mixture was refluxed for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, the solid matter formed during the reaction was filtered, and washed with water and methanol. The solids were dried in a vacuum oven to obtain 15 g (yield: 51%) of Compound-4.

compound- 5 of  Produce

15 g (9.4 mmol) of Compound-4 is dissolved in MC in a round bottom flask. 5.3 g (20.6 mmol) of silver trifluoromethanesulfonate is dissolved in isopropyl alcohol and added dropwise. After stirring at room temperature for one day, the solvent was removed and compound-5 was obtained, and the following reaction was carried out without purification.

compound- 6 of  Produce

To a round bottom flask was added phenyl Boro Nick Acid 23.5g (192.3 mmol), methyl 2-chloro-nicotinate 30 g (174.8 mmol), tetrakis (triphenylphosphine) palladium _{[Pd (PPh 3) 4]} 6.06 g (5.245 mmol) and potassium carbonate (48.31 g, 349 mmol) were dissolved in 600 mL of THF and 300 mL of distilled water, and the mixture was refluxed for 24 hours. When the reaction is complete, cool to room temperature and separate THF and distilled water. Add 600 mL of methanol to THF and crystallize. The resulting solid was filtered and washed with water and methanol. The solids were dried in a vacuum oven to obtain 32 g (yield: 86%) of Compound-6.

compound- 7's  Produce

Add 32 g (150 mmol) of Compound-6 to a round bottom flask and dissolve in 600 mL of anhydrous THF. Add 400 mL of the methylmagnesium bromide solution at 0 ° C to the flask. After completion of the reaction, the ammonium chloride is dissolved in 150 ml of water and quenched. The organic layer and the water layer are separated, and then all of the solvent is removed. 28 g (yield: 87%) of Compound-7 was obtained by using column chromatography.

compound- 8 of  Produce

In a round bottom flask under a nitrogen stream, compound 28 (137 mmol) is dissolved in MC solution, and 16.48 mL (131 mmol) of boron trifluoride diethylsulfate is added dropwise. After stirring for one day, water is added to dissolve the sodium bicarbonate. After completion of the reaction, the organic layer was separated, and then all of the solvent was removed. Then, 21 g (yield: 82%) of Compound-8 was obtained using hexane.

Compound D- 1 of  Produce

5 g (4.8 mmol) of Compound-5 and 2.8 g (14.5 mmol) of Compound-8 were placed in a round bottom flask and refluxed under nitrogen for one day. The resulting solid is filtered and washed three times with ethanol and hexane. The solid was dissolved in dichloromethane and then recrystallized with isopropyl alcohol to obtain 3 g (yield: 65%) of the compound D-1.

calcd. C ₅₆ H ₄₈ IrN ₃ : C, 70.41; H, 5.06; Ir, 20.12; N, 4.40; Found: C, 70.42; H, 5.11; N, 4.31;

Manufacturing example  2: D- 2 of  Produce

[Reaction Scheme 2]

compound- 9 of  Produce

9.8 g (50 mmol) of Compound-8, 6 g (20 mmol) of iridium chloride, 45 mL of 2-ethoxyethanol and 15 mL of distilled water were added to a round bottom flask and the mixture was refluxed for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, the solid matter formed during the reaction was filtered, and washed with water and methanol. The solids were dried in a vacuum oven to obtain 15 g (yield: 60%) of Compound-9.

compound- Ten  Produce

15 g (12 mmol) of Compound-9 is dissolved in MC in a round bottom flask. 6.9 g (26.7 mmol) of silver trifluoromethanesulfonate is dissolved in isopropyl alcohol and added dropwise. After stirring at room temperature for one day, the solvent was removed and Compound-10 was obtained, and the following reaction was carried out without purification.

Compound D- 2 of  Produce

Compound-107 g (8.2 mmol) and compound-3 (7.05 g, 24.7 mmol) were added to ethanol in a round bottom flask and refluxed under nitrogen for one day. The resulting solid is filtered and washed three times with ethanol and hexane. The solid was dissolved in dichloromethane and then recrystallized with isopropyl alcohol to obtain 4.5 g (yield: 63%) of the compound D-2. calcd. C ₄₉ H ₄₂ IrN ₃ : C, 68.03; H, 4.89; Ir, 22.22; N, 4.86; Found: C, 68.02; H, 4.95; N, 4.79;

Manufacturing example  3: D- 3 of  Produce

[Reaction Scheme 3]

compound- Eleven  Produce

To a round bottom flask was added 30 g (119.7 mmol) of methyl 5-bromo-2-chloropyridine-3-carboxylate, 13.43 g (131.7 mmol) of tertiarybutylboronic acid, and tetrakis (triphenylphosphine) 4.15 g (3.59 mmol) of Pd (PPh ₃ ) _{4 and} 33.1 g (239 mmol) of potassium carbonate were added to 600 mL of THF and 300 mL of distilled water, and the mixture was refluxed for 24 hours. When the reaction is complete, cool to room temperature and separate THF and distilled water. Add 600 mL of methanol to THF and crystallize. The resulting solid was filtered and washed with water and methanol. The solids were dried in a vacuum oven to obtain 20 g (yield: 73%) of Compound-11.

compound- 12 of  Produce

To a round bottom flask was added biphenyl-3-yl boronic acid 17.4 g (96.6 mmol), Compound -11 20 g (87.8 mmol), tetrakis (triphenylphosphine) palladium _{[Pd (PPh 3) 4]} 3 g (2.6 mmol) and potassium carbonate (24.2 g, 175 mmol) were dissolved in THF (400 mL) and distilled water (200 mL), and the mixture was refluxed for 24 hours. When the reaction is complete, cool to room temperature and separate THF and distilled water. Add 500 mL of methanol to THF and crystallize. The resulting solid was filtered and washed with water and methanol. The solids were dried in a vacuum oven to obtain 22 g (yield: 73%) of Compound-12.

compound- Thirteen  Produce

22 g (63.7 mmol) of compound-12 is added to a round bottom flask and dissolved in 400 mL of anhydrous THF. Add 169 mL of methylmagnesium bromide solution to the flask at 0 ° C. After completion of the reaction, the ammonium chloride is dissolved in 150 ml of water and quenched. The organic layer and the water layer are separated, and then all of the solvent is removed. Using column chromatography 18 g (Yield: 81%) of Compound-13 was obtained.

compound- 14 of  Produce

In a round bottom flask under a nitrogen stream, 18 g (52 mmol) of the compound-13 is dissolved in the MC solution, and then 6.54 mL (52 mmol) of boron trifluoride diethylsulfate is added dropwise. After stirring for one day, water is added to dissolve the sodium bicarbonate. After completion of the reaction, the organic layer was separated, and then all of the solvent was removed. 14 g (yield: 82%) of Compound-14 was obtained using hexane.

compound- Fifteen  Produce

13.7 g (41.8 mmol) of Compound-14, 5 g (16.7 mmol) of iridium chloride, 120 mL of 2-ethoxyethanol and 40 mL of distilled water were added to a round bottom flask and the mixture was refluxed for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, the solid matter formed during the reaction was filtered, and washed with water and methanol. The solid was dried in a vacuum oven to obtain 18 g (yield: 61%) of Compound-15.

compound- 16  Produce

18 g (10 mmol) of compound-15 is dissolved in MC in a round bottom flask. 5.8 g (22 mmol) of silver trifluoromethanesulfonate is dissolved in isopropyl alcohol and added dropwise. After stirring at room temperature for one day, the solvent was removed and Compound-16 was obtained, and the following reaction was carried out without purification.

Compound D- 3 of  Produce

7.1 g (6.3 mmol) of Compound-16 and 3.7 g (19.1 mmol) of Compound-8 were placed in a round bottom flask and refluxed under nitrogen for one day. The resulting solid is filtered and washed three times with ethanol and hexane. The solid was dissolved in dichloromethane and then recrystallized with isopropyl alcohol to give 5 g (yield: 45%) of compound D-3.

calcd. C ₆₂ H ₆₀ IrN ₃ : C, 71.65; H, 5.82; Ir, 18.49; N, 4.04; found: C, 71.62; H, 5.85; N, 4.01;

Manufacturing example  4: D- 4 of  Produce

[Reaction Scheme 4]

Compound D- 4 of  Produce

In a round bottom flask, compound -10 8 g (9.4 mmol) and compound-14 (9.2 g, 28 mmol) were added to ethanol and refluxed under nitrogen for one day. The resulting solid is filtered and washed three times with ethanol and hexane. The solid was dissolved in dichloromethane and then recrystallized with isopropyl alcohol to obtain 4.5 g (yield: 53%) of the compound D-4. calcd. C ₅₂ H ₄₈ IrN ₃ : C, 68.85; H, 5.33; Ir, 21.19; N, 4.63; Found: C, 68.82; H, 5.25; N, 4.70;

Manufacturing example  5: D- 5 of  Produce

[Reaction Scheme 5]

compound- 17  Produce

To a round bottom flask was added 35.2 g (177.7 mmol) of biphenyl-3-yl boronic acid, 30 g (161.6 mmol) of methyl 2-chloro-4-methylnicotinate in the presence of tetrakis (triphenylphosphine) palladium [ ₃ ) ₄ ] 5.6 g (4.85 mmol) of potassium carbonate and 44.67 g (323 mmol) of potassium carbonate were added to 600 mL of THF and 300 mL of distilled water, and the mixture was refluxed for 24 hours. When the reaction is complete, cool to room temperature and separate THF and distilled water. Add 600 mL of methanol to THF and crystallize. The resulting solid was filtered and washed with water and methanol. The solids were dried in a vacuum oven to obtain 40 g (yield: 81%) of Compound-17.

compound- 18  Produce

Add 40 g (132 mmol) of the compound-17 to a round bottom flask and dissolve in 800 mL of anhydrous THF. Add 351 mL of methylmagnesium bromide solution to the flask at 0 ° C. After completion of the reaction, ammonium chloride is dissolved in 200 ml of water and quenched. The organic layer and the water layer are separated, and then all of the solvent is removed. Using column chromatography, 34 g (yield: 85%) of Compound-18 was obtained.

compound- 19's  Produce

34 g (112 mmol) of Compound-18 was dissolved in MC solution in a round bottom flask under a nitrogen stream, and then 14 mL (112 mmol) of boron trifluoride diethylsulfate was added dropwise. After stirring for one day, water is added to dissolve the sodium bicarbonate. After completion of the reaction, the organic layer was separated, and then all of the solvent was removed. Then, 35 g (yield: 80%) of Compound-19 was obtained using hexane.

compound- Twenty  Produce

19.1 g (66.9 mmol) of the compound-19, 8 g (26.7 mmol) of iridium chloride, 90 mL of 2-ethoxyethanol and 30 mL of distilled water were added to a round bottom flask and the mixture was refluxed for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, the solid matter formed during the reaction was filtered, and washed with water and methanol. The solid was dried in a vacuum oven to obtain 30 g (yield: 70%) of Compound-20.

compound- 21  Produce

30 g (18.8 mmol) of Compound-20 is dissolved in MC in a round bottom flask. 10.6 g (41.3 mmol) of silver trifluoromethanesulfonate is dissolved in isopropyl alcohol and added dropwise. After stirring at room temperature for one day, the solvent was removed and Compound-21 was obtained, and the following reaction was carried out without purification.

Compound D- 5 of  Produce

12 g (11.6 mmol) of Compound-21 and 6.8 g (34.9 mmol) of Compound-8 were placed in a round bottom flask and refluxed under nitrogen at room temperature for one day. The resulting solid is filtered and washed three times with ethanol and hexane. The solid was dissolved in dichloromethane and then recrystallized with isopropyl alcohol to obtain 5 g (yield: 44%) of compound D-5.

calcd. C ₅₆ H ₄₈ IrN ₃ : C, 70.41; H, 5.06; Ir, 20.12; N, 4.40; Found: C, 70.35; H, 5.10; N, 4.35;

Manufacturing example  6: D- 6 of  Produce

[Reaction Scheme 6]

Compound D- 6 of  Produce

Compound -10 8 g (9.4 mmol) and compound-19 (8.1 g, 28.2 mmol) were added to ethanol in a round bottom flask and refluxed under nitrogen for one day. The resulting solid is filtered and washed three times with ethanol and hexane. The solid was dissolved in dichloromethane and then recrystallized with isopropyl alcohol to obtain 4.5 g (yield: 56%) of the compound D-6. calcd. C ₄₉ H ₄₂ IrN ₃ : C, 68.03; H, 4.89; Ir, 22.22; N, 4.86; Found: C, 68.02; H, 4.95; N, 4.75;

(Production of organic light emitting device)

Comparative Example  One

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum deposition machine. The prepared ITO transparent electrode was used as an anode to form HTM (a-NPD (4,4'-bis [N- (1-napthyl) -N-phenylamino] biphenyl ) Was vacuum-deposited to form a hole transport layer.

 [Z-1]

[Z-2]

(III) bis (4,6-difluorophenylpyridinato) tetrakis (4-fluorophenyl) pyridine represented by the following formula Z-3 as a blue phosphorescent dopant by using the CDBP represented by the formula Z- 1-pyrazolyl) borate was doped to 10 wt% and vacuum vapor deposited to form a 300 Å thick light emitting layer.

[Z-3]

Then, 50 Å of BAlq (bis (2-methyl-8-quinolinolato-N1, O8) - (1,1'-Biphenyl-4-olato) aluminum) represented by the following formula Z- 250 Å of Alq3 (tris (8-hydroxyquinolinato) aluminum) represented by the formula Z-5 were sequentially laminated to form an electron transport layer. LiF 5 Å and Al 1000 Å were successively vacuum deposited on the electron transport layer to form a cathode, thereby fabricating an organic light emitting device.

[Z-4]

[Z-5]

Comparative Example  2

In Comparative Example 1, a device was manufactured in the same manner as in Comparative Example 1, except that a dopant was used in place of the compound represented by the formula (Z-3).

[Chemical formula (T-1)

Comparative Example  3

In Comparative Example 1, a device was manufactured in the same manner as in Comparative Example 1, except that the dopant was replaced by the compound represented by the formula (T-2) instead of the compound represented by the formula (Z-3).

[Chemical Formula T-2]

Example  One

The same procedure as in Comparative Example 1 was carried out except that 10% by weight of a blue phosphorescent dopant was doped with the compound D-1 prepared in Preparation Example 1 instead of Fir6 represented by the above formula (Z-3) To prepare an organic light emitting device.

Example  2

An organic light emitting device was prepared in the same manner as in Example 1, except that the dopant according to Preparation Example 2 was used in place of the dopant according to Preparation Example 1.

Example  3

An organic light emitting device was fabricated in the same manner as in Example 1, except that the dopant according to Production Example 3 was used.

Example  4

An organic light emitting device was fabricated in the same manner as in Example 1 except that the dopant according to Production Example 4 was used.

Example  5

An organic light emitting device was fabricated in the same manner as in Example 1 except that a dopant according to Production Example 5 was used.

Example  6

An organic light emitting device was fabricated in the same manner as in Example 1, except that the dopant according to Production Example 6 was used.

(Performance Measurement of Organic Light Emitting Device)

For each of the organic light emitting devices manufactured in Examples 1 to 6 and Comparative Examples 1 to 3, current density change and luminance change according to the voltage were measured to evaluate the luminous efficiency and the lifetime characteristics. Specific measurement methods are as follows, and the results are shown in Table 1 below .

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current value flowing through the unit device was measured using a current-voltage meter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light emitting device manufactured, the luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) of the same brightness (9000 cd / m ² ) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

(4) Life evaluation

The lifetime was measured by measuring the time until the 3% luminous efficiency was reduced. The life of the materials provided in the present invention was relatively represented by 100% in the comparative example.

division The The luminous efficiency (cd / A) Device life (h)
T50 (%) at 10 mA / cm 2 Comparative Example 1 Z-3 6.1 One Comparative Example 2 T-1 5.4 100 Comparative Example 3 T-2 5.1 55 Example 1 D-1 10.5 98 Example 2 D-2 9.8 105 Example 3 D-3 11.6 111 Example 4 D-4 8.7 125 Example 5 D-5 9.9 107 Example 6 D-6 10.7 99

As shown in Table 1, it can be seen that the device manufactured using the material provided in the present invention is much better in luminous efficiency or lifetime. This shows the possibility that the compound prepared in the present invention can be used as a material for a good organic light emitting device.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: organic light emitting device 200: organic light emitting device
105: organic layer
110: cathode
120: anode
130: light emitting layer 230: light emitting layer
140: hole assist layer

Claims (13)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ¹ to R ⁶ are each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted silyl group,
Wherein one of R ¹ to R ³ is a substituted or unsubstituted C6 to C30 aryl group,
Any one of R ⁴ to R ⁶ is a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted silyl group,
X ¹ and X ² are each independently O, S, SO, SO ₂ , POR ⁷ , NR ⁸ , CR ⁹ R ¹⁰ , or SiR ¹¹ R ¹² ,
Wherein R ⁷ to R ¹² are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 hetero An arylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C30 aryloxycar A substituted or unsubstituted C1 to C30 sulfamoylamino group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C2 to C30 alkynyl group, A substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C1 to C20 acyloxy group, a substituted or unsubstituted C1 to C20 acylamino group, a substituted or unsubstituted C1 to C20 acyl group, A substituted or unsubstituted C1 to C30 alkylthiol group, a substituted or unsubstituted C1 to C30 heterocyclic thiol group, a substituted or unsubstituted C6 to C30 arylthiol group, a substituted or unsubstituted C1 to C30 arylthiol group, A halogen atom, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a perorenyl group or a substituted or unsubstituted C1 to C30 heteroarylthiol group Or
R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are fused to form a ring,
M is Ir, Os, Pt, Pb, Re, Ru, or Pd,
n And m are each independently any one of integers 1 and 2, and n + m is an integer of 3. The method according to claim 1,
Wherein any one of R ¹ to R ³ is a substituted or unsubstituted C6 to C10 aryl group. The method according to claim 1,
Wherein any one of R ¹ to R ³ is a substituted or unsubstituted phenyl group. The method according to claim 1,
Wherein any one of R ⁴ to R ⁶ is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted silyl group, Or an unsubstituted phenyl group. 5. The method of claim 4,
Wherein any one of R ⁴ to R ⁶ is an unsubstituted methyl group, an unsubstituted ethyl group, an isopropyl group, a t-butyl group, a trimethylsilyl group, or an unsubstituted phenyl group. The method according to claim 1,
Wherein X ¹ and X ² are each independently O, S, POR ⁷ , NR ⁸ , CR ⁹ R ¹⁰ , or SiR ¹¹ R ¹² ,
Wherein each of R ⁷ to R ¹² is independently a C1 to C4 alkyl group. The method according to claim 1,
Any one of R ¹ to R ³ is a substituted or unsubstituted phenyl group,
Any one of R ⁴ to R ⁶ is an unsubstituted methyl group, an unsubstituted ethyl group, an isopropyl group, a t-butyl group, a trimethylsilyl group, or an unsubstituted phenyl group,
X ¹ and X ² are each independently CR ⁹ R ¹⁰ ,
Wherein R ⁹ and R ¹⁰ are each independently a C1 to C4 alkyl group. 8. The method of claim 7,
Wherein R < ^{1 >} is an unsubstituted phenyl group,
R ⁵ is an unsubstituted methyl group, an unsubstituted ethyl group, an isopropyl group, a t-butyl group, or a trimethylsilyl group,
And each of R ⁹ and R ¹⁰ is independently a methyl group. The method according to claim 1,
Wherein the compound of Formula 1 is one of the compounds listed in Group I below.
[Group I]

An anode and a cathode facing each other, and
And at least one organic layer positioned between the anode and the cathode,
Wherein the organic layer comprises a compound according to any one of claims 1 to 9. 11. The method of claim 10,
Wherein the organic layer includes a light emitting layer,
Wherein the light emitting layer comprises the compound. 12. The method of claim 11,
Wherein the compound is included as a dopant of the light emitting layer. A display device comprising the organic opto-electronic device according to claim 10.

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