KR101966280B1 - Novel organometallic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel organometallic compound and an organic light emitting device using the same.

Description

TECHNICAL FIELD The present invention relates to a novel organometallic compound and an organic light emitting device using the same.

The present invention relates to a novel organometallic compound and an organic light emitting device comprising the same.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research has been conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. The organic material layer may have a multilayer structure composed of different materials in order to improve the efficiency and stability of the organic light emitting device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

There is a continuing need for the development of new materials for the organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel organometallic compound and an organic light emitting device comprising the same.

The present invention provides an organometallic compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

M is iridium (Ir), platinum (Pt), osmium (Os), titanium (Ti), zirconium (Zr), or hafnium

R ₁ to R ₃ and R ₁₁ to R ₁₃ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a substituted or unsubstituted C _1-60 heterocyclic group containing at least one heteroatom selected from the group consisting of N, O and S,

a1 is an integer of 0 to 7,

a2 and a3 are each independently an integer of 0 to 4,

b is an integer of 1 to 8,

a1 + b is 8 or less,

n is 1, 2, or 3;

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes an organic electroluminescent Device.

The organometallic compound represented by Formula 1 can be used as a material of an organic material layer of an organic light emitting device and can improve the efficiency, the driving voltage and / or the lifetime of the organic light emitting device. In particular, the organometallic compound represented by Formula 1 may be included in the light emitting layer and used as a phosphorescent dopant.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The present invention provides an organometallic compound represented by the above formula (1).

는 다른 치환기에 연결되는 결합을 의미한다. In the present specification,

Quot; means a bond connected to another substituent.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one heteroatom selected from the group consisting of N, O and S, or a substituted or unsubstituted heterocyclic group having at least two heteroatoms selected from the group consisting of N, O and S, Or unsubstituted. For example, when the "substituent group to which two or more substituents are connected" is a biphenyl group, the biphenyl group may be an aryl group substituted with one phenyl group, or may be interpreted as a substituent group in which two phenyl groups are connected.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, , An indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above. In the present specification, the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group. In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present specification, the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heterocyclic ring is not a monovalent group and two substituents are bonded to each other.

In the above formula (1), M may be iridium (Ir).

In Formula 1, R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-10 alkyl; Or substituted or unsubstituted C _6-10 aryl.

For example, R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, amino, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, Butyl, sec-butyl, phenyl, biphenyl, terphenyl, or naphthyl.

Specifically, for example, R ₁ may be hydrogen.

Specifically, for example, R ₂ and R ₃ may each independently be hydrogen, methyl, ethyl or phenyl.

In formula (1), a1 to a3 may each independently be 0, 1, 2, or 3. For example, a1 to a3 may each independently be 0 or 1.

In the above formula (1), R ₁₁ to R ₁₃ may each independently be substituted or unsubstituted C _1-10 alkyl.

For example, R ₁₁ to R ₁₃ are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, amino, methyl, ethyl, propyl, n-propyl, isopropyl, -Butyl, or sec-butyl.

Specifically, for example, R ₁₁ to R ₁₃ may be methyl.

In Formula 1, b may be 1, 2, or 3. For example, b may be one.

Here, a1 represents the number of R ₁ , and when a ₁ is 2 or more, two or more R _{1 s} may be the same or different from each other. a2 and a3 can be understood with reference to the description of a1 and the structure of the formula (1).

B represents SiR ₁₁ R ₁₂ R ₁₃ , and when b is 2 or more, two or more SiR ₁₁ R ₁₂ R ₁₃ may be the same or different from each other.

On the other hand, the organometallic compound may be any one selected from the group consisting of the following formulas (1-1) to (1-8)

In the above formulas 1-1 to 1-8,

R ₁ to R ₃ and R ₁₁ to R ₁₃ , a 1 to a 3 and n are the same as defined in the above formula (1).

For example, the organometallic compound may be selected from the group consisting of the following compounds.

The organometallic compound represented by Formula 1 includes benzoquinoline having at least one silyl group as a ligand, and the life characteristics of the organic light emitting device using the same can be prolonged.

Here, the organometallic compound represented by Formula 1 may be prepared through a ligand exchange reaction as shown in Schemes 1 to 3 below, but is not limited thereto. The above production method can be more specific in the production example to be described later.

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

The reaction can be carried out in a polar solvent, specifically, in an alcoholic solvent such as methanol, ethanol and the like.

It is possible to prepare the organometallic compound represented by the above formula (1) to be prepared by appropriately substituting the starting materials with reference to the structures of the above Schemes (1) to (3) and (1).

Also, the present invention provides an organic light-emitting device comprising the organometallic compound represented by Formula 1. In one embodiment, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes an organic electroluminescent Device.

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include an organic metal compound represented by the general formula (1). In the light emitting layer, the organometallic compound represented by Formula 1 may serve as a dopant.

Specifically, the organometallic compound represented by Formula 1 may be included as a phosphorescent dopant in the light emitting layer.

At this time, the light emitting layer may further include a known host. Specifically, the weight ratio of the host to the organometallic compound represented by Formula 1 in the light emitting layer may be 99: 1 to 80:20, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, in the organic light emitting device of the present invention, in addition to the light emitting layer as the organic material layer, a hole injecting layer and a hole transporting layer between the first electrode and the light emitting layer, and an electron transporting layer and an electron injecting layer between the light emitting layer and the second electrode are further included . ≪ / RTI > However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic layers.

Meanwhile, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig. In this structure, the organic metal compound represented by Formula 1 may be included in the light emitting layer.

2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is. In such a structure, the organic metal compound represented by Formula 1 may be included in at least one of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer. Preferably, the organometallic compound represented by Formula 1 may be included in the light emitting layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers contains an organometallic compound represented by the above formula (1). In addition, when the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and then depositing a material usable as a cathode on the organic material layer. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the organic metal compound represented by Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted to the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferred that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

The dopant material may further include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, and the like in addition to the organometallic compound represented by the formula (1). Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Do. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has an ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

The organic metal compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The preparation of the compound represented by Formula 1 and the organic light emitting device comprising the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[Manufacturing Example]

Production Example 1-1 Synthesis of Intermediates A1 and B1

(1) Preparation of intermediate 1-1a

(54.0 g, 0.21 mol), 4,4,5,5-tetramethyl- [1,3,2] dioxaborane (58.5 g, 0.23 mol), Pd (dppf) Cl ₂ (1.53 g, 2.09 mmol) and KOAc (61.6 g, 0.62 mol) were added to 830 mL of dioxane and the mixture was stirred at reflux for 8 hours. The temperature was lowered to room temperature and the solvent was concentrated under reduced pressure. The concentrate was completely dissolved in CHCl ₃ and washed with water. The solution in which the product was dissolved was concentrated under reduced pressure and purified by column chromatography. Intermediate 1-1a was obtained (52.8 g, yield 82%, MS: [M + H] < ⁺ > = 306).

(2) Preparation of intermediate A1

Intermediate 1-1a (52.8 g, 173 mmol) and chlorotrimethylsilane (20.6 g, 190 mmol) were dissolved in 600 mL of tetrahydrofuran under a nitrogen atmosphere, followed by addition of a 2M aqueous potassium carbonate solution (250 mL) and tetrakis- Palladium (3.8 g, 3.46 mmol) was added thereto, followed by stirring at reflux for 14 hours. After the completion of the reaction, the temperature was lowered, and the aqueous layer was separated and the organic layer was removed. After dissolving it with CHCl ₃ , it was washed with water. Magnesium sulfate and acidic clay were added and stirred, followed by filtration and concentration under reduced pressure. Thereafter, the compound A1 was isolated by column chromatography under the hexane condition. (35.0 g, 80% yield, MS: [M + H] < ⁺ > = 252).

(3) Preparation of intermediate 1-1b

Iodide chloride (12 g, 40.2 mmol) and Compound A1 (25.3 g, 0.10 mmol) were dissolved in 1000 ml of 2-ethoxyethanol and 330 ml of distilled water, and the mixture was heated and stirred for 18 hours. The temperature was lowered to room temperature, filtered, and washed with 3 L of ethanol to prepare solid compound 1-1b (30.7 g, yield 52%).

.

(4) Preparation of intermediate B1

AgOTf (14.6 g, 0.057 mol) in which Intermediate 1-1b (30.7 g, 0.021 mol) and methylene chloride (800 ml) were dissolved was dissolved in 400 ml of methanol, and the mixture was stirred at room temperature while blocking light. After filtration after 24 hours, the filtered filtrate was blown off and Toluene precipitated to obtain Compound B1 (yield: 91%) without further purification.

Production Example 1-2: Synthesis of Compound of Intermediate A2 and B2

(1) Preparation of intermediate 1-1c

The compound 1-1c was prepared in the same manner as Intermediate 1-1a except that 6-bromobenzo [h] quinoline (50.0 g) was used instead of 3-bromobenzo [h] quinoline (47.3 g, yield 80 %, MS: [M + H] < ⁺ > = 306).

(2) Preparation of intermediate A2

(30.1 g, yield 77%, MS: [M + H] < ⁺ > = 252) was prepared in the same manner as Intermediate A1 except that Intermediate 1-1c was used instead of Intermediate 1-1a.

(3) Preparation of intermediate 1-1d

Intermediate 1-1d was prepared in the same manner as Intermediate 1-1b except that Intermediate A2 was used instead of Intermediate A1 (28.8 g, yield 49%).

(4) Preparation of intermediate B2

Intermediate B2 (90% yield) was prepared in the same manner as Intermediate B1, except that Intermediate 1-1d was used instead of Intermediate 1-1b

Production Example 1-3: Synthesis of Compound A3 and Compound B3

(1) Preparation of intermediate 1-1e

The compound 1-1c was prepared in the same manner as Intermediate 1-1a except that 7-bromobenzo [h] quinoline (50.0 g) was used instead of 3-bromobenzo [h] quinoline (46.5 g, yield 79 %, MS: [M + H] < ⁺ > = 306).

(2) Preparation of intermediate A3

(29.5 g, yield 77%, MS: [M + H] < ⁺ > = 252) was prepared in the same manner as Intermediate A3 except for using Intermediate 1-1e instead of Intermediate 1-1a.

(3) Preparation of intermediate 1-1f

Intermediate 1-1f was prepared in the same manner as Intermediate 1-1b except that Intermediate A3 was used instead of Intermediate A1 (26.1 g, yield 48%).

(4) Preparation of intermediate B3

Intermediate B3 (yield 92%) was prepared in the same manner as Intermediate B1, except that Intermediate 1-1f was used instead of Intermediate 1-1b

Production Example 1-4: Synthesis of Compound of Intermediate A4 and B4

(1) Preparation of Intermediate 1-1g

Compound 1-1g was prepared in the same manner as Intermediate 1-1a except that 8-bromobenzo [h] quinoline (50.0 g) was used instead of 3-Bromobenzo [h] quinoline (47.1 g, yield 80 %, MS: [M + H] < ⁺ > = 306).

(2) Preparation of intermediate A4

Intermediate A4 was prepared (30.3 g, yield 78%, MS: [M + H] ⁺ = 252) in the same manner as Intermediate A1 except that Intermediate 1-1a was used instead of Intermediate 1-1a.

(3) Preparation of intermediate 1-1h

Intermediate 1-1h was prepared in the same manner as Intermediate 1-1b except that Intermediate A3 was used instead of Intermediate A1 (30.2 g, yield 46%).

(4) Preparation of intermediate B4

Intermediate B4 (yield 91%) was prepared in the same manner as Intermediate B1, except that Intermediate 1-1h was used instead of Intermediate 1-1b

Production Example 2

Production example 2-1: Synthesis of compound of intermediate D1

(1) Preparation of intermediate 2-1b

Intermediate 2-1b was prepared (20.1 g, yield 50%) in the same manner as Intermediate 1-1b except that 2-phenylpyridine (Compound C1) was used instead of Intermediate A1.

(2) Preparation of intermediate D1

Intermediate D1 (14.2 g) was prepared in the same manner as Intermediate B1, except that Intermediate 2-1b was used instead of Intermediate 1-1b

Production example 2-2: Synthesis of compound of intermediate C2 and D2

(1) Preparation of intermediate 3-1a

After dissolving 2,4-dibromopyridine (35.0 g, 0.15 mol) and phenylboronic acid (20.20 g, 0.16 mol) in 300 mL of tetrahydrofuran in a nitrogen atmosphere, 1.5 M aqueous potassium carbonate solution (150 mL) was added And tetrakis- (triphenylphosphine) palladium (3.44 g, 2.98 mmol) was added thereto, followed by heating and stirring for 11 hours. The intermediate 3-1a was prepared (29.1 g, yield 84%, MS: < RTI ID = 0.0 > [M + H] < ⁺ > = 233).

(2) Preparation of intermediate C2

(23.8 g, yield 83%, MS: [M + H] < ⁺ > = 232) was prepared in the same manner as Intermediate 3-1a except that Intermediate C2 was used in place of 2,4-dibromopyridine. .

(3) Preparation of intermediate 3-1b

Intermediate 3-1b was prepared (19.1 g, yield 55%) in the same manner as Intermediate 1-1b, except that Intermediate C2 (15.8 g) was used instead of Intermediate Al.

(4) Preparation of intermediate D2

Intermediate D2 (11.1 g) was prepared in the same manner as Intermediate B1 except for using Intermediate 3-1b instead of Intermediate 1-1b

Production Example 2-3: Synthesis of Compound of Intermediate C3 and D3

(1) Preparation of intermediate C3

(51.0 g, yield 86%, MS: [M + H 2]) was prepared in the same manner as Intermediate 3-1a except that 2-bromo-4-methylpyridine was used instead of 2,4-dibromopyridine ] ⁺ = 170).

(2) Preparation of intermediate 4-1b

Intermediate 4-1b was prepared in the same manner as Intermediate 1-1b except that Intermediate C3 (26.4 g) was used instead of Intermediate Al (32.1 g, yield 50%).

(3) Preparation of intermediate D3

Intermediate D3 (20.0 g) was prepared in the same manner as Intermediate B1 except for using Intermediate 4-1b instead of Intermediate 1-1b

Production Example 2-4: Synthesis of Intermediates C4 and D4

(1) Preparation of intermediate 4-1a

Intermediate 4-1a was prepared in the same manner as Intermediate 3-1a except that 2,5-dibromopyridine was used instead of 2,4-dibromopyridine (30.1 g, yield 87%, MS: [M + H ] ⁺ = 234).

(2) Preparation of intermediate C4

(24.9 g, yield 83%, MS: [M + H] < ⁺ >) was prepared in the same manner as Intermediate 3-1a, except that Intermediate 4-1a was used instead of 2,4-dibromopyridine. 232).

(2) Preparation of intermediate 5-1b

Intermediate 5-1b was prepared in the same manner as Intermediate 1-1b except that Intermediate C4 (15.0 g) was used instead of Intermediate Al (17.8 g, yield 49%).

(4) Preparation of intermediate D4

Intermediate D4 (10.3 g) was prepared in the same manner as Intermediate B1 except that Intermediate 5-1b was used instead of Intermediate 1-1b

Production example 2-5: Synthesis of compound of intermediate C5 and D5

(1) Preparation of intermediate 5-1a

Intermediate 5-1a was prepared in the same manner as Intermediate 3-1a except that 2,5-dibromo-4-methylpyridine was used instead of 2,4-dibromopyridine (30.4 g, yield 88%, MS: [M + H] < ⁺ > = 248).

(2) Preparation of intermediate C5

The compound C5 was prepared in the same manner as Intermediate 3-1a except that Intermediate 5-1a was used instead of 2,4-dibromopyridine (24.2 g, yield 81%, MS: [M + H] ⁺ = 246).

(3) Preparation of intermediate 6-1b

Intermediate 6-1b was prepared (16.5 g, yield 48%) in the same manner as Intermediate 1-1b except for using Intermediate C5 (15.0 g) instead of Intermediate Al.

(4) Preparation of intermediate D5

Intermediate D5 (9.8 g) was prepared in the same manner as Intermediate B1, except that Intermediate 6-1b was used instead of Intermediate 1-1b

Production Example 2-6: Synthesis of Compound C6 and D6

(1) Preparation of intermediate C6

Compound C6 was prepared in the same manner as Intermediate 3-1a except that 2-bromopyridine and [1,1'-biphenyl] -4-ylboronic acid were used instead of 2,4-dibromopyridine and phenylboronic acid (36.2 g, yield 82%, MS: [M + H] < ⁺ > = 232).

(2) Preparation of intermediate 7-1b

Intermediate 7-1b was prepared in the same manner as Intermediate 1-1b except that Intermediate C6 (15.5 g) was used instead of Intermediate A1 (19.0 g, yield 51%).

(3) Preparation of intermediate D6

Intermediate D6 (11.2 g) was prepared in the same manner as Intermediate B1, except that Intermediate 7-1b was used instead of Intermediate 1-1b

Preparation Example 2-7: Synthesis of the compounds of Intermediates C7 and D7

(1) Preparation of intermediate C7

Compound C7 was prepared in the same manner as Intermediate 3-1a except that 2-bromopyridine and [1,1'-biphenyl] -3-ylboronic acid were used instead of 2,4-dibromopyridine and phenylboronic acid (37.5 g, 85% yield, MS: [M + H] < ⁺ > = 232).

(2) Preparation of Intermediate 8-1b

Intermediate 8-1b was prepared (18.4 g, yield 53%) in the same manner as Intermediate 1-1b except that Intermediate C7 (14.6 g) was used instead of Intermediate Al.

(3) Preparation of intermediate D7

Intermediate D7 (10.2 g) was prepared in the same manner as Intermediate B1, except that Intermediate 8-1b was used instead of Intermediate 1-1b

Production Example 3-1: Synthesis of Compound 1 Compound

The compound B1 (8.5 g, 9.40 mmol), the compound C1 (3.6 g, 23.5 mmol), 55 ml of MeOH and 55 ml of EtOH were placed in a nitrogen atmosphere and stirred at a reaction temperature of 90 ° C for 48 hours. After completion of the reaction, the reaction mixture was filtered and purified by column chromatography under the conditions of ethyl acetate: hexane = 1: 6 to prepare Compound 1 (yield 41%).

Production Example 3-2: Synthesis of Compound 2 Compound

Compound 2 (yield 39%) was prepared in the same manner as Compound 1 except that Intermediate C5 was used instead of Intermediate C1.

Production Example 3-3: Synthesis of Compound 3 Compound

Compound 3 (yield 42%) was prepared in the same manner as Compound 1 except that Intermediate C7 was used instead of Intermediate C1.

Production Example 3-4: Synthesis of Compound 4 Compound

Compound 4 (yield: 37%) was prepared in the same manner as Compound 1 except for using Intermediate B2 and Intermediate C2 instead of Intermediate B1 and Intermediate C1.

Production Example 3-5: Synthesis of Compound 5 Compound

Compound 5 (yield 39%) was prepared in the same manner as Compound 1 except that Intermediate B3 and Intermediate C4 were used instead of Intermediate B1 and Intermediate C1.

Production Example 3-6: Synthesis of Compound 6 Compound

Compound 6 (yield: 38%) was prepared in the same manner as in the preparation of compound 1, except for using intermediate B4 and intermediate C3 instead of intermediate B1 and intermediate C1.

Production Example 3-7: Synthesis of Compound 7 Compound

Compound 7 (yield: 37%) was prepared in the same manner as Compound 1 except for using Intermediate D1 and Intermediate A1 instead of Intermediate B1 and Intermediate C1.

Production Example 3-8: Synthesis of Compound 8 Compound

Compound 8 (yield 40%) was prepared in the same manner as compound 1 except for using intermediate D2 and intermediate A1 instead of intermediate B1 and intermediate C1.

Production Example 3-9: Synthesis of Compound 9 Compound

Compound 9 (yield 38%) was prepared in the same manner as in the preparation of compound 1, except for using Intermediate D3 and Intermediate A1 instead of Intermediate B1 and Intermediate C1.

Production Example 3-10: Synthesis of Compound 10 Compound

Compound 10 (42% yield) was prepared in the same manner as Compound 1 except that Intermediate D4 and Intermediate Al were used instead of Intermediate B1 and Intermediate C1.

Production Example 3-11: Synthesis of Compound 11 Compound

Compound 11 (yield 40%) was prepared in the same manner as compound 1 except for using Intermediate D2 and Intermediate A2 instead of Intermediate B1 and Intermediate C1.

Production Example 3-12: Synthesis of Compound 12 Compound

Compound 12 (yield 42%) was prepared in the same manner as Compound 1 except that Intermediate D5 and Intermediate A2 were used instead of Intermediate B1 and Intermediate C1.

Production Example 3-13: Synthesis of Compound 13 Compound

Compound (13) (yield 40%) was prepared in the same manner as Compound 1 except for using Intermediate D6 and Intermediate A2 instead of Intermediate B1 and Intermediate C1.

Production Example 3-14: Synthesis of Compound 14 Compound

Compound 14 (yield: 37%) was prepared in the same manner as compound 1 except for using Intermediate D3 and Intermediate A3 instead of Intermediate B1 and Intermediate C1.

Production Example 3-15: Synthesis of Compound 15 Compound

Compound 15 (yield 39%) was prepared in the same manner as Compound 1 except that Intermediate D5 and Intermediate A3 were used instead of Intermediate B1 and Intermediate C1.

Production Example 3-16: Synthesis of Compound 16 Compound

Compound 16 (yield 38%) was prepared in the same manner as Compound 1 except for using Intermediate D7 and Intermediate A3 instead of Intermediate B1 and Intermediate C1.

Production Example 3-17: Synthesis of Compound 17 Compound

Compound (17) (yield 35%) was prepared in the same manner as Compound 1 except that Intermediate D1 and Intermediate A4 were used instead of Intermediate B1 and Intermediate C1.

Production Example 3-18: Synthesis of Compound 18 Compound

Compound 18 (yield 39%) was prepared in the same manner as Compound 1 except that Intermediate D4 and Intermediate A4 were used instead of Intermediate B1 and Intermediate C1.

Production Example 3-19: Synthesis of Compound 19 Compound

Compound 19 (43% yield) was prepared in the same manner as Compound 1 except that Intermediate Al was used instead of Intermediate C1.

Production Example 3-20: Synthesis of Compound 20 Compound

Compound 20 (44% yield) was prepared in the same manner as Compound 1 except that Intermediate B3 and Intermediate A3 were used instead of Intermediate B1 and Intermediate C1.

Example 1

A thin glass substrate coated with ITO (indium tin oxide) at a thickness of 1,300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following hexanitrile hexaazatriphenylene (HAT) compound was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 50 Å to form a hole injection layer. N-phenylamino] biphenyl (NPB; HT-1), which is a material for transporting holes, was thermally vacuum deposited to a thickness of 250 Å to form a hole transport layer And an HT-2 compound was vacuum deposited on the HT-1 vapor deposition layer to a thickness of 50 Å to form an electron blocking layer. Compound H1 and H2 as a host and compound 1 as a phosphorescent dopant prepared in Production Example 3-1 were co-deposited on the HT-2 deposited film at a weight ratio of 44:44:12 to form a 400Å thick light emitting layer. An ET-1 material was vacuum deposited on the light-emitting layer to a thickness of 250 ANGSTROM and an ET-2 material was co-deposited with a 2% weight ratio Li to a thickness of 100 ANGSTROM to form an electron transport layer and an electron injection layer. Aluminum was deposited on the electron injecting layer to a thickness of 1000 to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of aluminum was maintained at 2 Å / sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr Thus, an organic light emitting device was fabricated.

Examples 2 to 9

The organic light emitting devices of Examples 2 to 9 were fabricated in the same manner as in Example 1, except that the compound described in Table 1 was used instead of Compound 1 as the phosphorescent dopant.

Comparative Examples 1 to 3

Organic light-emitting devices of Comparative Examples 1 to 3 were fabricated in the same manner as in Example 1, except that the compound described in Table 1 was used instead of Compound 1 as a dopant.

Experimental Example 1

The voltage, efficiency, color coordinates, and lifetime were measured by applying current to the organic light emitting devices fabricated in Examples 1 to 9 and Comparative Examples 1 to 3, and the results are shown in Table 1 below.

T95 means the time required for the luminance to be reduced to 95% from the initial luminance.

Dopant
matter Voltage
(V
@ 10 mA / cm ² ) efficiency
(cd / A
@ 10 mA / cm ² ) Color coordinates
(x, y) life span
(T95, h,
@ 50 mA / cm ² ) Example 1 One 3.3 80 (0.443, 0.520) 151 Example 2 2 3.1 81 (0.420, 0.534) 221 Example 3 3 3.05 79 (0.386, 0.539) 237 Example 4 4 3.09 79 (0.422, 0.530) 201 Example 5 6 3.2 80 (0.445, 0.518) 176 Example 6 7 3.1 80 (0.446, 0.515) 230 Example 7 9 3.3 78 (0.352, 0.531) 170 Example 8 13 3.2 80 (0.358, 0.520) 208 Example 9 19 3.3 83 (0.445, 0.511) 183 Comparative Example 1 YGD 3.53 67 (0.45, 0.54) 140 Comparative Example 2 E1 3.44 71 (0.44, 0.54) 100 Comparative Example 3 E2 3.52 75 (0.44, 0.55) 112

As can be seen from the above Table 1, when the compound of the present invention was used as a phosphorescent dopant, it was confirmed that the phosphorescent dopant exhibited excellent lifetime characteristics in comparison with the comparative example using the compounds of E1 and E2. It was confirmed that the TMS substituent affects the lifetime. In the case of Examples 2 to 4, 6 and 8, the life characteristics were improved by about two times or more as compared with Comparative Example 2. From these results, it can be seen that the life time difference is remarkable depending on the presence or absence of the silyl substituent and the substitution position.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: Hole injection layer 6: Hole transport layer
7: light emitting layer 8: electron transporting layer

Claims (9)

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

In Formula 1,
M is iridium (Ir)
R < ₁ > is hydrogen,
R ₂ and R ₃ are each independently hydrogen, methyl, ethyl or phenyl,
R ₁₁ to R ₁₃ are methyl,
a1 is an integer of 0 to 7,
a2 and a3 are each independently an integer of 0 to 4,
b is 1,
a1 + b is 8 or less,
n is 1, 2, or 3;
delete delete delete delete The method according to claim 1,
Wherein said compound is any one selected from the group consisting of the following chemical formulas 1-1 to 1-8:

In the above formulas 1-1 to 1-8,
R ₁ to R ₃ and R ₁₁ to R ₁₃ , a 1 to a 3 and n are as defined in claim 1.
The method according to claim 1,
Wherein the compound is any one selected from the group consisting of the following compounds:

A first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes at least one of the organic material layers of any one of claims 1, 6, and 7 Wherein the organic metal compound is an organic metal compound.
9. The method of claim 8,
Wherein the organic layer includes a light emitting layer,
Wherein the organic metal compound is included as a phosphorescent dopant of the light emitting layer.

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