WO2019221487A1 - Compound and organic light emitting diode comprising same - Google Patents

Abstract

The present specification relates to compounds of chemical formulas 101 to 105 and an organic light emitting diode comprising same.

Description

Compound and organic light emitting device comprising same

The present invention claims the benefit of the filing date of Korean Patent Application No. 10-2018-0055103 filed with the Korea Intellectual Property Office on May 14, 2018, the entire contents of which are incorporated herein.

The present specification relates to a compound and an organic light emitting device including the same.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

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

The present specification provides a compound and an organic light emitting device including the same.

According to an exemplary embodiment of the present specification to provide a compound represented by any one of formulas 101 to 105.

[Formula 101]

[Formula 102]

[Formula 103]

[Formula 104]

[Formula 105]

In Chemical Formulas 101 and 102,

One of X ₃ and X ₄ is N, the other is CR,

In Chemical Formulas 103 and 104,

One of X ₁ and X ₄ is N, the other is CR,

In Chemical Formula 105,

One of X ₁ and X ₂ is N, the other is CR,

In Chemical Formulas 101 to 105,

M is Ir or Pt,

A is a substituted or unsubstituted 6-membered hydrocarbon ring, or a substituted or unsubstituted 5- or 6-membered hetero ring,

L1 and L2 combine with each other to form a substituted or unsubstituted ring,

R1 and R are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted An aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted arylamine group, or a substituted or unsubstituted phosphine oxide group, or adjacent substituents combine with each other to form a ring,

n is an integer from 0 to 6,

l is an integer from 0 to 4,

m is 1 or 2, o is 1 or 2, m + o ≦ 3,

When n and l are plural, R1 is the same as or different from each other,

When m and o are plural, the ligands in parentheses are the same or different from each other.

In addition, the present specification is an organic light emitting device comprising a first electrode, a second electrode and at least one organic layer provided between the first electrode and the second electrode, wherein at least one layer of the at least one organic layer is the chemical formula. It provides an organic light emitting device comprising a compound of 101 to 105.

The compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting diode, and by using the same, it is possible to improve the efficiency, high color purity, and lifetime characteristics in the organic light emitting diode.

1 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.

2 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.

[Description of the code]

1: substrate

2: first electrode

3: organic material layer

4: light emitting layer

5: second electrode

Hereinafter, this specification is demonstrated in detail.

The present specification provides a compound represented by Formulas 101 to 105.

The structure of the chemical formula can increase the strength of the bond between the ligand and the metal and reduce the vibration level, it can provide a high light emission efficiency while reducing the half width. In addition, as the position of the substituent of R1 moves away from the metal atom, the size of the molecule increases, which prevents aggregation between the dopants, reducing the self-quenching effect and increasing the lifetime. Therefore, by using the structure of the present invention as a light emitting material of the organic material layer it is possible to improve the efficiency, high color purity and life characteristics in the organic light emitting device.

In the above formula, the ligand including L1 and L2 is a structure in parentheses represented by the repeating number m

Is different in structure. Homogeneous ligand complexes in which all ligands are identical, that is, containing three identical ligands have the same direction of luminescence, whereas heterogeneous ligand complexes containing ligands of different structures have a higher luminescence orientation in the vertical direction, thereby improving efficiency of luminescence. high. Therefore, in Chemical Formula 1, m is preferably 1 or 2.

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components unless specifically stated otherwise.

As used herein, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.

As used herein, the term "substituted or unsubstituted" is deuterium; Nitrile group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heteroaryl group, or two or more of the substituents exemplified above are substituted with a substituent, or means that does not have any substituents. For example, "a substituent to which two or more substituents are linked" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heteroaryl group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be a linear or branched alkyl group, it may be a cycloalkyl group. Although carbon number is not specifically limited, It is preferable that it is 1-30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto. The cyclic alkyl group may include a cycloalkyl group having 3 to 30 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, penalenyl group, perrylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. no.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group are thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolinyl group (phenanthroline), isooxazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzofuranyl group and the like, but is not limited thereto.

In the present specification, the hydrocarbon ring means an aromatic or aliphatic hydrocarbon ring, it may be a six-membered ring. Examples of the aryl group described above may be applied except that the aromatic hydrocarbon ring is not a monovalent group.

In the present specification, the heterocycle means an aromatic or aliphatic ring including one or more heteroatoms, and may be a 5- or 6-membered ring. Examples of the heteroaryl group described above may be applied except that the heterocycle is not a monovalent group.

According to an exemplary embodiment of the present disclosure, wherein M is Ir.

According to an exemplary embodiment of the present disclosure, wherein R is hydrogen.

According to an exemplary embodiment of the present specification, R1 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present specification, R1 is hydrogen; heavy hydrogen; Or an alkyl group unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, R1 is hydrogen; Or an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is hydrogen, a linear alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, terbutyl group, pentyl group, or hexyl group.

For example, according to an exemplary embodiment of the present invention, when the compounds of the present invention are represented by the following formulas 101-1 to 105-1, the size of the molecule becomes larger as the position of the substituent of R1 moves away from the metal atom. It can prevent the agglomeration of metals and reduce the self quenching effect and increase the life.

 [Formula 101-1]

 [Formula 102-1]

 [Formula 103-1]

 [Formula 104-1]

 [Formula 105-1]

In Chemical Formulas 101-1 to 105-1, the definitions of X1 to X4, L1, L2, R1, A, M, m, and o are as defined in Chemical Formulas 101 to 105,

n is an integer from 0 to 4,

l is an integer of 0 to 2.

According to an exemplary embodiment of the present specification, the L1 and L2 may be bonded to each other to form a structure of the formula 1-1 or 1-2 including M.

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

M is Ir or Pt,

Ra to Rk are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted Aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted arylamine group, or substituted or unsubstituted phosphine oxide group.

According to an exemplary embodiment of the present specification, Ra to Rc are the same as or different from each other, and each independently, hydrogen; heavy hydrogen; Or an alkyl group unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, Ra to Rc are the same as or different from each other, and each independently, hydrogen; Or an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Ra to Rc are the same as or different from each other, and each independently hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms; Or a cycloalkyl group having 3 to 8 carbon atoms.

According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms; Or a cycloalkyl group having 3 to 8 carbon atoms, and Rc is hydrogen.

According to an exemplary embodiment of the present specification, Ra and Rb are the same as each other, a straight chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms; Or a cycloalkyl group having 3 to 8 carbon atoms, and Rc is hydrogen.

According to an exemplary embodiment of the present specification, Ra to Rc are the same as each other, and a linear alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, the Rd to Rk are the same as or different from each other, and each independently, hydrogen; heavy hydrogen; Or an alkyl group unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, Re and Ri are the same as or different from each other, and each independently, an alkyl group unsubstituted or substituted with deuterium, Rf is hydrogen; heavy hydrogen; Or an alkyl group unsubstituted or substituted with deuterium, and Rd, Rg, Rh, Rj and Rk are hydrogen or deuterium.

According to an exemplary embodiment of the present specification, Re and Ri have an alkyl group unsubstituted or substituted with deuterium, Rf is hydrogen; An alkyl group unsubstituted or substituted with deuterium, and Rd, Rg, Rh, Rj and Rk are hydrogen.

According to an exemplary embodiment of the present specification, the

May be represented by the following Chemical Formula 106 or the following Chemical Formula 107.

[Formula 106]

[Formula 107]

In Chemical Formulas 106 and 107,

* Is a site which binds to M of Formulas 101 to 105,

Ra to Rk are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted Aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted arylamine group, or substituted or unsubstituted phosphine oxide group,

o is 1 or 2,

When o is 2, the ligands in parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, m is 1.

According to an exemplary embodiment of the present specification, m is 2.

According to an exemplary embodiment of the present specification, m is 1 or 2, m + o is 3.

According to an exemplary embodiment of the present disclosure, wherein m is 2, o is 1.

According to an exemplary embodiment of the present specification, A is a 6-membered hydrocarbon ring, or 5 or 6 membered hetero ring, the 6-membered hydrocarbon ring or 5 or 6-membered hetero ring is deuterium, nitrile, halogen group, It is unsubstituted or substituted with any one or more substituents selected from the group consisting of an alkyl group, an alkyl group substituted with deuterium, an aryl group, a heteroaryl group, and an arylamine group.

According to an exemplary embodiment of the present specification, A is a 6-membered hydrocarbon ring, or 5 or 6 membered hetero ring, the 6-membered hydrocarbon ring or 5 or 6 membered hetero ring is deuterium; Or an alkyl group unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, A is a benzene ring, or a 5-membered monocyclic heterocycle, and the benzene ring or a 5-membered monocyclic heterocycle is deuterium; Or an alkyl group unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, A is a benzene ring unsubstituted or substituted with an alkyl group or an alkyl group substituted with deuterium; Or a thiazole group unsubstituted or substituted with an alkyl group substituted with an alkyl group or deuterium.

According to an exemplary embodiment of the present specification, A is an benzene ring unsubstituted or substituted with one or more alkyl groups or alkyl groups substituted with deuterium; Or a thiazole group unsubstituted or substituted with an alkyl group substituted with an alkyl group or deuterium.

According to an exemplary embodiment of the present specification, A is a benzene ring unsubstituted or substituted with one or more alkyl groups of 1 to 6 carbon atoms or an alkyl group of 1 to 6 carbon atoms substituted with deuterium; Or a thiazole group unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms substituted with deuterium.

According to an exemplary embodiment of the present specification, A is a benzene ring unsubstituted or substituted with one or two alkyl groups of 1 to 6 carbon atoms or an alkyl group of 1 to 6 carbon atoms substituted with deuterium; Or a thiazole group unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms substituted with deuterium.

According to an exemplary embodiment of the present specification, the

May be represented by the following Chemical Formula 108 or the following Chemical Formula 109.

[Formula 108]

[Formula 109]

In Chemical Formulas 108 and 109,

* Is a moiety linked to a ring where M and X1 to X4 of Formulas 101 to 105 are located,

Rm and Rn are each hydrogen; heavy hydrogen; Or an alkyl group unsubstituted or substituted with deuterium, a is an integer of 0 to 4, and when a is plural, Rm is the same as or different from each other.

According to an exemplary embodiment of the present specification, Rm and Rn are each an alkyl group having 1 to 6 carbon atoms unsubstituted or substituted with deuterium, and a is 0, 1 or 2.

According to yet an embodiment of the present disclosure, the compound of Formula 101 to 105 may be represented by the following structural formula.

By properly combining the formulas described in the examples herein and the intermediates based on common technical knowledge, all of the compounds of the present invention described herein can be prepared.

The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.

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, the organic light emitting device of the present invention includes a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including one or two or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers may include the compound described above.

However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIG. 1, but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which a first electrode 2, an organic material layer 3, and a second electrode 4 are sequentially stacked on a substrate 1. In FIG. 1, the organic material layer 3 may include the compound of the present invention.

2 illustrates a structure of an organic light emitting device in which a first electrode 2, an organic material layer 3, a light emitting layer 4, and a second electrode 5 are sequentially stacked on a substrate 1. The emission layer 4 of FIG. 2 may include the compound of the present invention. The organic layer 3 may further include a layer having additional functions in addition to the light emitting layer, such as a hole injection layer, a hole transport layer, or an electron blocking layer.

It is not limited to the structure of FIG. 2, and may further include an additional organic material layer, such as a hole blocking layer, an electron transport layer, or an electron injection layer, between the light emitting layer 4 and the second electrode 5.

The organic light emitting device of the present invention may include a structure in which a first electrode, an organic material layer, and a second electrode are sequentially stacked on a substrate, and the organic material layer may include the compound of the present invention.

In one embodiment of the present specification, the organic material layer may include one or more emission layers, and one or more layers of the one or more emission layers may include the compound of the present invention.

According to a specific example, the organic light emitting device according to the exemplary embodiment of the present invention may have a structure in which an anode, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode are sequentially stacked, wherein the hole transport layer and the light emitting layer are interposed therebetween. The electronic blocking layer provided in the, and may further include a hole blocking layer provided between the light emitting layer and the electron transport layer. In addition, the semiconductor device may further include a p-type doping layer provided between the anode and the hole transport layer and including a p-type dopant. The electron transport layer may include an n-type dopant. The p-type dopant and the n-type dopant may be included in an amount of 1 to 40% by weight based on 100% by weight of the corresponding layer. As the p-type dopant and the n-type dopant, those known in the art may be used. For example, as the n-type dopant, an alkali metal complex such as Liq may be used.

In one embodiment of the present specification, the light emitting layer including the compound of the present invention is a red light emitting layer.

In one embodiment of the present specification, the compound of the present invention is included as a dopant in a light emitting layer.

In one embodiment of the present specification, the compound of the present invention is included in the light emitting layer including the compound in an amount of 1 part by weight to 20 parts by weight based on a total of 100 parts by weight of the light emitting layer including the compound.

According to one embodiment of the present specification, the light emitting layer including the compound of the present invention may include an additional host material. As an example, the emission layer may include a compound of Formula (B).

[Formula B]

In Chemical Formula B,

Ara and Arb are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with a heteroaryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group,

R ₁₀₁ and R ₁₀₂ are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; An aryl group unsubstituted or substituted with a heteroaryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group, or adjacent groups combine with each other to form a substituted or unsubstituted aromatic hydrocarbon ring, and b and c are each an integer of 0 to 4.

According to one example, Formula B may be represented by the following Formula B-1.

[Formula B-1]

In Formula B-1, the definitions of Ara, Arb, R101, R102, and c are as described above, and d is an integer of 0 to 6.

According to an example, Ara is an N-containing heterocycle substituted with an aryl group, and Arb is an aryl group.

According to another example, Ara is a quinazoline group substituted with a phenyl group, and Arb is a phenyl group.

In one embodiment of the present specification, the compound of the present invention is included in at least one layer of a hole injection layer, a hole transport layer, a hole injection and transport at the same time and a hole control layer.

In one embodiment of the present specification, the compound of the present invention is included in at least one of an electron injection layer, an electron transport layer, a layer for simultaneously injecting and transporting an electron, and an electron control layer.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

According to one embodiment of the present specification, the compound of the present invention may be prepared according to the following scheme, but is not limited thereto. In the following schemes, the type and number of substituents can synthesize various kinds of intermediates as those skilled in the art appropriately select known starting materials. Reaction type and reaction conditions may be used those known in the art.

[Scheme]

In the above scheme, the definitions of X to X4, A and Ra to Rc are as described above. As required,

Instead, a ligand having a pyridine structure can be used.

Fabrication of the organic light emitting device using the compound of the present invention will be described in detail in the following Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[ Production Example ]

Preparation Example 1 Preparation of Intermediate 1

In a three-necked flask, 10-chloro-3- (3,5-dimethylphenyl) benzo [f] quinoxaline (20.0 g, 62.7 mmol), isobutylboronic acid (7.0 g, 69.0 mmol), Pd (OAc) ₂ ( 0.6 g, 2.5 mmol), PCy ₃ (1.4 g, 5.0 mmol) and K ₃ PO ₄ (40.0 g, 188.2 mmol) were added together with 200 ml of toluene and stirred for 8 hours under reflux conditions under argon. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered using a celite plug, the filtrate was concentrated, and the sample was purified by silica gel column chromatography, and distilled and purified to obtain 13.2 g of Intermediate 1. (Yield 62%, MS [M + H] ⁺ = 340)

Production Example  2: Preparation of Intermediate 2

10-chloro-4- (3,5-dimethylphenyl) benzo [h] quinazoline (20.0 g, 62.7 mmol), Iron (III) acetylacetonate (1.1 g, 3.1 mmol), tetra 400 ml of hydrofuran and 40 ml of NMP were added, and 2.0 M isopropyl magnesium chloride tetrahydrofuran solution (63 ml, 125.5 mmol) was slowly added dropwise while stirring at 0 ° C. under a nitrogen atmosphere. When the dropwise addition was completed, the mixture was stirred for 3 hours while maintaining at 0 ° C. After the reaction was completed, water was slowly added, transferred to a separating funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ , filtered and concentrated, and then the sample was purified by silica gel column chromatography and distilled to obtain 11.3 g of intermediate 2. (Yield 55%, MS [M + H] ⁺ = 326)

Preparation Example 3 Preparation of Intermediate 3

1- (3,5-bis (methyl-d3) phenyl) -8-chlorobenzo [f] quinazoline (20.0 g, 61.6 mmol), isobutyl boronic acid (6.9 g, 67.7 mmol), Pd (OAc) ₂ (0.6 g, 2.5 mmol), PCy ₃ (1.4 g, 4.9 mmol) and K ₃ PO ₄ (39.2 g, 184.7 mmol) were added together with 200 ml of toluene and stirred for 8 hours under reflux conditions under argon. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered using a celite plug, the filtrate was concentrated, and the sample was purified by silica gel column chromatography, and distilled and purified to obtain 14.3 g of Intermediate 3. (Yield 67%, MS [M + H] ⁺ = 347)

Preparation Example 4 Preparation of Intermediate 4

1) Preparation of Intermediate 4-a

300 ml of tetrahydrofuran in a 3-necked flask with 3-bromo-10-chlorobenzo [f] quinoxaline (20.0 g, 68.1 mmol) and (3- (tert-butyl) phenyl) boronic acid (13.3 g, 74.9 mmol) It was dissolved in K ₂ CO ₃ (37.7g, 272.5mmol) was dissolved in 150ml H ₂ O. Pd (PPh ₃ ) ₄ (3.1 g, 2.7 mmol) was added thereto, and the mixture was stirred for 8 hours under argon atmosphere reflux conditions. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel and extracted with water and ethyl acetate. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to give 17.0 g of intermediate 4-a. (Yield 72%, MS [M + H] ⁺ = 347)

2) Preparation of Intermediate 4

Intermediate 4-a (17.0 g, 49.0 mmol), K ₃ PO _{4 in} a three neck flask (31.2 g, 147.0 mmol) was dissolved in 340 ml of toluene and 34 ml of H ₂ O. Nitrogen purge the reaction for 20 minutes and use 2,4,6-trimethyl-1,3,5,2,4,6-trioxatrivoryne (7.54 ml, 53.9 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.5 mmol) and S-Phos (2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl) (0.8 g, 2.0 mmol) was added and stirred for 18 hours under reflux conditions under argon. After the reaction was completed, the mixture was cooled to room temperature, 200 ml of water was added to the separatory funnel, and the organic layer was extracted. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 10.2 g of intermediate 4. (Yield 64%, MS [M + H] ⁺ = 326)

Production Example  5: Preparation of Intermediate 5

In a three-necked flask, 4-chloro-6,7,10-trimethylbenzo [h] quinazoline (13.0 g, 50.6 mmol) and (3- (tert-butyl) phenyl) boronic acid (9.9 g, 55.7 mmol) It was dissolved in 195 ml of hydrofuran and K ₂ CO ₃ (28.0 g, 202.5 mmol) was dissolved in 98 ml of H ₂ O. Pd (PPh ₃ ) ₄ (2.3 g, 2.0 mmol) was added thereto, followed by stirring for 8 hours under reflux condition of argon atmosphere. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with water and ethyl acetate. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to give 10.5 g of intermediate 5. (Yield 60%, MS [M + H] ⁺ = 347)

Preparation Example 6 Preparation of Intermediate 6

1) Preparation of Intermediate 6-a

300 ml of tetrahydrofuran with 2-bromo-10-chlorobenzo [h] quinazolin (20.0 g, 68.1 mmol) and (4- (tert-butyl) phenyl) boronic acid (13.3 g, 74.9 mmol) in a three neck flask It was dissolved in K ₂ CO ₃ (37.7g, 272.5mmol) was dissolved in 150ml H ₂ O. Pd (PPh ₃ ) ₄ (3.1 g, 2.7 mmol) was added thereto, and the mixture was stirred for 8 hours under an argon atmosphere reflux condition. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with water and ethyl acetate. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to give 17.7 g of intermediate 6-a. (Yield 75%, MS [M + H] ⁺ = 347)

2) Preparation of Intermediate 6

Intermediate 6-a (17.0 g, 49.0 mmol), K ₃ PO _{4 in} a three-necked flask (31.2 g, 147.0 mmol) was dissolved in 340 ml of toluene and 34 ml of H ₂ O. Nitrogen purge the reaction for 20 minutes and use 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborane (7.54 ml, 53.9 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.5 mmol) and S-Phos (2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl) (0.8 g, 2.0 mmol) was added and stirred for 18 hours under reflux conditions under argon. After the reaction was completed, the mixture was cooled to room temperature, 200 ml of water was added to the separatory funnel, and the organic layer was extracted. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 10.7 g of intermediate 6. (Yield 67%, MS [M + H] ⁺ = 326)

Preparation Example 7 Preparation of Compound 1-a

1) Preparation of Compound 1-a

Into a three-necked flask with intermediate 1 (10.0g, 29.4mmol), iridium (III) chloride hydrate (5.0g, 12.9mmol) 135ml of _2- ethoxyethanol, 45ml of H ₂ O and stirred for 12 hours under reflux conditions under argon atmosphere It was. After the reaction was completed, the reaction mixture was cooled to room temperature, the precipitate was filtered, washed with methanol, dried, and used in the next reaction without further purification. (13.0g, yield 98%)

2) Preparation of Compound 1

Compound 1-a (13.0 g, 7.2 mmol), 2,2,6,6-tetramethylheptan-3,5-dione (13.2 g, 71.7 mmol), K ₂ CO ₃ (9.9 g, 71.7) in a three neck flask mmol) and 90 ml of 2-ethoxyethanol were added and stirred at room temperature for 24 hours. After the reaction was completed, after filtration, washed with MeOH, dissolved in CH ₂ Cl ₂ and filtered using a plug of celite. Thereafter, the mixture was recrystallized with CH ₂ Cl ₂ and isopropyl alcohol, and finally 4.8 g of Compound 1 was obtained through a sublimation tablet. (Yield 32%, MS [M + H] ⁺ = 1054)

Production Example  8: Preparation of Compound 2

Compound 1, except that Intermediate 2 was used instead of Intermediate 1 in Preparation Example 7, and 3,7-diethylnonane-4,6-dione was used instead of 2,2,6,6-tetramethylheptan-3,5-dione. 5.0 g of Compound 2 was prepared by the same method as the preparation method of. (MS [M + H] ⁺ = 1054)

Production Example  9: Preparation of Compound 3

Compound 1 of Preparation 1, except that Intermediate 3 was used instead of Intermediate 1, and 2,8-dimethylnonane-4,6-dione was used instead of 2,2,6,6-tetramethylheptan-3,5-dione. 4.8 g of Compound 3 was prepared by the same method as the preparation method. (MS [M + H] ⁺ = 1066)

Production Example  10: Preparation of Compound 4

4.9 g of Compound 4 was prepared by the same method as the method of preparing Compound 1, except that Intermediate 4 was used instead of Intermediate 1 in Preparation Example 7. (MS [M + H] ⁺ = 1026)

Production Example  11: Preparation of Compound 5

Compound 1, except that Intermediate 5 was used instead of Intermediate 1 in Preparation Example 7, and 3,7-diethylnonane-4,6-dione was used instead of 2,2,6,6-tetramethylheptan-3,5-dione. 4.9 g of Compound 5 was prepared by the same method as the preparation method of (MS [M + H] ⁺ = 1111).

Production Example  12: Preparation of Compound 6

4.9 g of Compound 6 was prepared by the same method as the method of preparing Compound 1, except that Intermediate 6 was used instead of Intermediate 1 in Preparation Example 7. (MS [M + H] ⁺ = 1026)

Experimental Example

Experimental Example 1

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) having a thickness of 1,400Å was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. Fischer Co. Decon ™ CON705 product was used as a detergent, and distilled water was filtered secondly with a 0.22 μm sterilizing filter from Millerpore Co .. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic washing with a solvent of isopropyl alcohol, acetone and methanol for 10 minutes, dried and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

A mixture of 95 wt% of HT-A and 5 wt% of P-DOPANT was thermally vacuum deposited to a thickness of 100 kPa on the prepared ITO transparent electrode. Then, only HT-A was deposited to a thickness of 1150 kPa to form a hole transport layer. The following HT-B was thermally vacuum deposited to a thickness of 950 kPa on the hole transport layer to form an electron blocking layer. Subsequently, a mixture of 98% by weight of RH and 2% by weight of [Compound 1] with a dopant was vacuum deposited to a thickness of 360 kPa on the electronic blocking layer to form a light emitting layer. Subsequently, the following ET-A was vacuum deposited to a thickness of 50 kPa on the light emitting layer to form a hole blocking layer. Next, the following ET-B and Liq are mixed in a weight ratio of 2: 1 on the hole blocking layer to form a electron transport layer by thermal vacuum layering at a thickness of 250 kPa, followed by mixing LiF and magnesium in a weight ratio of 1: 1. The vacuum injection was carried out to a thickness of 50 kHz to form an electron injection layer. The organic light emitting device was manufactured by mixing magnesium and silver on the electron injection layer in a weight ratio of 1: 4, and depositing the same to a thickness of 170 Å to form a cathode.

Experimental Examples 2 to 6

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound shown in Table 1 instead of the compound 1.

Comparative Examples 1 to 7

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound shown in Table 1 instead of the compound 1. In Table 1 below, RD-1 to RD-7 are as follows.

Voltage, efficiency, emission spectrum, and lifetime (T97) were measured by applying current to the organic light emitting diodes manufactured in the Experimental Example and Comparative Experimental Example, and the results are shown in Table 1 below. Here, voltage and efficiency were measured by applying a current density of 10 mA / cm ² , and the full width at half maximum was measured from the obtained emission spectrum. The lifetime T97 means the time until the initial luminance drops to 97% at a current density of 20 mA / cm ² . Each value is represented by the relative ratio with respect to the value of the comparative example 1.

	Dopant	Voltage (V)	EQE` (%)	Half width (nm)	Life (T97, hr)
Experimental Example 1	Compound 1	0.98	1.32	0.90	1.06
Experimental Example 2	Compound 2	1.01	1.11	0.72	1.04
Experimental Example 3	Compound 3	0.99	1.24	0.76	1.07
Experimental Example 4	Compound 4	1.03	1.29	0.88	1.11
Experimental Example 5	Compound 5	1.00	1.16	0.73	1.21
Experimental Example 6	Compound 6	1.02	1.21	0.78	1.13
Comparative Example 1	RD-1	1.00	1.00	1.00	1.00
Comparative Example 2	RD-2	1.82	0.47	1.32	0.31
Comparative Example 3	RD-3	1.25	0.89	0.95	0.83
Comparative Example 4	RD-4	1.35	0.85	1.21	0.61
Comparative Example 5	RD-5	1.23	0.76	1.15	0.76
Comparative Example 6	RD-6	1.04	0.98	0.75	0.57
Comparative Example 7	RD-7	1.05	0.97	0.78	0.59

The compound of the present invention has a structure in which one more nitrogen element serving as an electron acceptor is contained in the quinoline structure of Comparative Example 1, and one more phenyl ring serving as an electron donor is condensed. It can be seen that these two effects cancel each other to have an appropriate energy level to have a voltage similar to that of Comparative Example 1. When the energy level is changed, the voltage is increased by trapping electrons or holes, and the wavelength is changed, so that the red light emitting device does not perform properly.

Compounds of the present invention increase the bond strength between the ligand and the metal to reduce the vibration level, which leads to a decrease in the half width and high efficiency at the same time. In addition, as the position of the substituent of R1 moves away from the metal atom, the size of the molecule increases, which prevents aggregation between dopants and decreases the self-quenching effect, thereby increasing the lifetime.

In addition, homologous ligand complexes such as RD-2 of Comparative Example 2 have a uniform direction of luminescence, whereas heteroligand complexes such as compounds of Compounds 1 to 6 have a higher luminescence orientation in the vertical direction, resulting in higher luminescence efficiency.

In the case of Comparative Example 3 in which the portion corresponding to A in Formulas 101 to 105 of the present invention is benzofuran, it can be seen that, in the case of phenyl, relatively high voltage, low efficiency, and low lifetime are shown.

In Comparative Examples 4 and 5, the number of nitrogen elements serving as electron acceptors is different from the present invention, which results in higher voltage, lower efficiency, and lower lifetime compared to the compound of the present invention.

In Comparative Examples 6 and 7, it can be seen that the lifetime is shorter than when Compound 2 having different positions of alkyl substituents is used in the same core structure (Experimental Example 2).

Therefore, as shown in Table 1, when the materials of the present invention are utilized as the light emitting layer dopant of the organic EL device, a high efficiency, high color purity and long life device can be obtained.

Claims (9)

1. A compound represented by any one of the following Formulas 101 to 105:

   [Formula 101]

   

   [Formula 102]

   

   [Formula 103]

   

   [Formula 104]

   

   [Formula 105]

   

   In Chemical Formulas 101 and 102,

   One of X ₃ and X ₄ is N, the other is CR,

   In Chemical Formulas 103 and 104,

   One of X ₁ and X ₄ is N, the other is CR,

   In Chemical Formula 105,

   One of X ₁ and X ₂ is N, the other is CR,

   In Chemical Formulas 101 to 105,

   M is Ir or Pt,

   A is a substituted or unsubstituted 6-membered hydrocarbon ring, or a substituted or unsubstituted 5- or 6-membered hetero ring,

   L1 and L2 combine with each other to form a substituted or unsubstituted ring,

   R1 and R are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted An aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted arylamine group, or a substituted or unsubstituted phosphine oxide group, or adjacent substituents combine with each other to form a ring,

   n is an integer from 0 to 6,

   l is an integer from 0 to 4,

   m is 1 or 2, o is 1 or 2, m + o ≦ 3,

   When n and l are plural, R1 is the same as or different from each other,

   When m and o are plural, the ligands in parentheses are the same or different from each other.
2. The method according to claim 1, wherein A is a 6-membered hydrocarbon ring, or 5 or 6 membered hetero ring, the 6-membered hydrocarbon ring or 5 or 6 membered hetero ring is deuterium, nitrile, halogen, alkyl, Compound substituted or unsubstituted with any one or more substituents selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group and an arylamine group substituted with deuterium.
3. The method according to claim 1, wherein

   

   Is a compound represented by the following formula 106 or 107:

   [Formula 106]

   

   [Formula 107]

   

   In Chemical Formulas 106 and 107,

   * Is a site which binds to M of Formulas 101 to 105,

   Ra to Rk are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted Aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted arylamine group, or substituted or unsubstituted phosphine oxide group,

   o is 1 or 2,

   When o is 2, the ligands in parentheses are the same or different from each other.
4. The method according to claim 1,

   

   Is a compound represented by Formula 108 or 109:

   [Formula 108]

   

   [Formula 109]

   

   In Chemical Formulas 108 and 109,

   * Is a moiety linked to a ring where M and X1 to X4 of Formulas 101 to 105 are located,

   Rm and Rn are each hydrogen; heavy hydrogen; Or an alkyl group unsubstituted or substituted with deuterium,

   a is an integer of 0 to 4, and when a is plural, Rm is the same as or different from each other.
5. The compound of claim 1, wherein Formulas 101 to 105 are any one selected from the following compounds:

   

   

   

   

   
6. An organic light emitting device comprising a first electrode, a second electrode and at least one organic material layer provided between the first electrode and the second electrode, wherein the compound according to any one of claims 1 to 5 Organic light-emitting device that is contained in one or more layers of the organic material layer.
7. The organic light emitting device of claim 6, wherein the organic material layer includes one or more light emitting layers, and one or more layers of the one or more light emitting layers include the compound.
8. The organic light emitting device of claim 7, wherein the light emitting layer including the compound is a red light emitting layer.
9. The organic light emitting device of claim 7, wherein the compound is included in the light emitting layer including 1 part by weight to 20 parts by weight based on a total of 100 parts by weight of the light emitting layer including the compound.

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