KR102643057B1 - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel compound with excellent thermal stability and luminescent performance, and an organic electroluminescent device with improved properties such as luminous efficiency, driving voltage, and lifespan by including the same in one or more organic layers.

Description

Organic light-emitting compound and organic electroluminescent device using the same {ORGANIC LIGHT-EMITTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

Beginning with the observation of organic thin film luminescence by Bernanose in the 1950s, research on organic electroluminescent (EL) devices continued, leading to blue electroluminescence using anthracene single crystals in 1965, and Tang in 1987. ) presented an organic electroluminescent device with a layered structure divided into a hole layer and a functional layer of the light-emitting layer. Since then, in order to create high-efficiency, long-life organic electroluminescent devices, there has been development in the form of introducing each characteristic organic material layer within the device, leading to the development of specialized materials used for this.

In an organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer from the anode, and electrons are injected into the organic material layer from the cathode. When the injected hole and electron meet, an exciton is formed, and when this exciton falls to the ground state, light is emitted. At this time, the material used as the organic material layer can be classified into light-emitting material, hole injection material, hole transport material, electron transport material, electron injection material, etc., depending on its function.

Light-emitting materials can be divided into blue, green, and red light-emitting materials according to their emission color, and yellow and orange light-emitting materials to achieve better natural colors. Additionally, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system can be used as a luminescent material.

Dopant materials can be divided into fluorescent dopants using organic materials and phosphorescent dopants using metal complex compounds containing heavy atoms such as Ir and Pt. At this time, because the development of phosphorescent materials can theoretically improve luminous efficiency by up to 4 times compared to fluorescence, much research is being conducted on phosphorescent host materials as well as phosphorescent dopants.

To date, hole injection layer and hole transport layer. NPB, BCP, Alq ₃ , etc. are widely known as hole blocking layer and electron transport layer materials, and anthracene derivatives are reported as light emitting layer materials. In particular, metal complex compounds containing Ir, such as Firpic, Ir(ppy) ₃ , and (acac)Ir(btp) ₂ , which have advantages in terms of efficiency improvement among light emitting layer materials, produce blue, green, and red colors. (red) is used as a phosphorescent dopant material, and 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent host material.

However, although conventional organic layer materials have advantages in terms of luminescence characteristics, their glass transition temperature is low and their thermal stability is very poor, so they are not at a satisfactory level in terms of the lifespan of organic electroluminescent devices. Therefore, the development of organic layer materials with excellent performance is required.

The purpose of the present invention is to provide a novel organic compound that can be applied to organic electroluminescent devices and has excellent thermal stability and luminescent performance.

Another object of the present invention is to provide an organic electroluminescent device with low driving voltage, high luminous efficiency, and improved lifespan including the novel organic compound.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1) or formula (2).

In Formulas 1 to 2,

R ₁ and R ₂ are the same as or different from each other, and each independently represents a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, and a C ₆ to C ₄₀ aryl group. , heteroaryl group with 5 to 40 nuclear atoms, aryloxy group with C ₆ to C ₄₀ , alkyloxy group with C ₁ to C ₄₀ , cycloalkyl group with C ₃ to C ₄₀ , heterocyclo with 3 to 40 nuclear atoms. Alkyl group, C ₆ ~ C ₄₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ arylphos It is selected from the group consisting of a pin group, an arylphosphine oxide group of C ₆ to C ₄₀ and an arylsilyl group of C ₆ to C ₄₀ , or R ₁ and R ₂ are combined to form a polycyclic condensed ring represented by the following formula (3) can be formed,

In Formula 3 above,

* is a site connected to R ₁ and R ₂ of Formula 1 or 2, respectively,

Ring A is a monocyclic or polycyclic alicyclic ring, a monocyclic or polycyclic heteroalicyclic ring, a monocyclic or polycyclic aromatic ring, or a monocyclic or polycyclic heteroaromatic ring,

Y ₁ to Y ₁₆ are each independently CR ₆ or N,

Here, a plurality of R ₆ are the same or different from each other and can form a ring by combining with other adjacent R ₆ ,

R ₃ to R ₆ are the same or different from each other, and are each independently hydrogen, deuterium, halogen, cyano group, nitro group, sulfonyl group (SO ₂ ), C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkene. Nyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group , C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group. , C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ arylphosphine oxide group, and C ₆ ~ C ₄₀ arylsilyl group,

a to c are each independently an integer of 0 to 3, where when a to c are each independently 0, R ₃ to R ₆ are each independently hydrogen, and when a to c are 1 to 3, R ₃ to R ₆ has the above-mentioned substituents excluding hydrogen,

In R ₁ to R ₆ an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, aryl The boron group, arylphosphine group, arylphosphine oxide group, and arylamine group each independently contain deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ to C ₆₀ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphine group, C ₆ to C ₆₀ arylphosphine oxide group, and C ₆ to C ₆₀ arylamine group. In this case, when substituted with a plurality of substituents, they may be the same or different from each other.

In addition, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers is represented by Formula 1 or Formula 2. An organic electroluminescent device comprising the indicated compound is provided.

According to the present invention, the compound represented by Formula 1 or 2 has excellent heat resistance, carrier transport ability, luminescence ability, etc., and can be used as an organic layer material of an organic electroluminescent device.

In addition, the organic electroluminescent device containing the compound according to the present invention can produce an organic electroluminescent device with excellent luminous performance, lifespan, efficiency, and low driving voltage compared to conventional materials, and furthermore, a full-color display with improved performance and lifespan. Panels can also be manufactured.

Hereinafter, the present invention will be described in detail.

<New organic compounds>

The new organic compound according to the present invention has a structure in which triphenylene or phenanthrene and fluorene are combined as a basic skeleton (core), and is characterized by being represented by the above formula (1) or (2).

In this way, the core structure of the present invention in which triphenylene or phenanthrene and fluorene are bonded can suppress planarity due to steric hindrance of the condensed ring bonded to the fluorene, thereby lowering the crystallinity of the compound. . In addition, since it has triplet (T1) and singlet (S1) values similar to triphenylene, the energy difference between them (T1-S1) can be reduced. In other words, it is possible to solve the crystallinity problem of conventional triphenylene and at the same time compensate for the difference in T1-S1 value of conventional fluorene.

In addition, various substituents, especially aryl groups/heteroaryl groups, are introduced into the basic skeleton to significantly increase the molecular weight of the compound, thereby improving the glass transition temperature and thus having higher thermal stability than conventional CBP. Therefore, a device containing the compound of Formula 1 according to the present invention can greatly improve durability and lifespan characteristics.

In addition, the compound of Formula 1 or 2 can control HOMO and LUMO energy levels depending on the type of substituent introduced into the above-mentioned basic skeleton, can have a wide band gap, and can have high carrier transport properties. For example, when an electron withdrawing group (EWG) with high electron absorption, such as a nitrogen-containing heterocycle (e.g., pyridine group, pyrimidine group, triazine group, etc.) is bonded to the basic skeleton, the entire molecule is bipolar. ) characteristics, it can increase the binding force between holes and electrons. As such, the compound of Formula 1 in which EWG is introduced into the basic skeleton has excellent carrier transport properties and excellent light-emitting properties, so it can be used as an electron injection/transport layer material or a lifespan improvement layer material in addition to the light-emitting layer material of an organic electroluminescent device. can be used

Furthermore, when the compound of Formula 1 or 2 according to the present invention is adopted as a hole injection/transport layer material, electron injection/transport layer material, and blue, green, and/or red phosphorescent host material of an organic EL device, the efficiency and It can demonstrate a far superior effect in terms of lifespan. Therefore, the compound according to the present invention can greatly contribute to improving the performance and lifespan of organic EL devices. In particular, this improvement in device lifespan has a great effect on maximizing performance in full-color organic light emitting panels.

In the present invention, the compound represented by Formula 1 has a structure in which phenylene and fluorene groups are bonded as its basic skeleton, and the compound represented by Formula 2 has a structure in which phenanthrene and fluorene groups are bonded as its basic skeleton.

In the compound represented by Formula 1 or 2, R ₁ and R ₂ may be combined with each other to form a condensed ring in the form of a polycyclic ring common in the art, or may not form a condensed ring.

According to one embodiment of the present invention, when R ₁ and R ₂ do not form a condensed ring, R ₁ and R ₂ are the same as or different from each other, and each independently represents an alkyl group of C ₁ to C ₄₀ , C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~C ₄₀ alkyloxy group, C ₃ ~C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ ~C ₄₀ arylamine group, C ₁ ~C ₄₀ alkylsilyl group, C ₁ ~C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ arylphosphine oxide group and C ₆ ~ C ₄₀ arylsilyl group may be selected from the military.

Here, when R ₁ and R ₂ do not form a condensed ring, it is preferable that at least one of Y ₁ to Y ₁₀ described below is N.

According to another embodiment of the present invention, R ₁ and R ₂ may form a condensed ring represented by Formula 3 above.

More specifically, when R ₁ and R ₂ form a condensed ring, the compound represented by Formula 1 or 2 of the present invention may be further specified as the following Formula 1-A or 2-A, respectively.

[Formula 1-A]

[Formula 2-A]

Ring A may be a conventional hydrocarbon-based ring known in the art or a hydrocarbon-based ring containing one or more heteroatoms, and other rings to which they are adjacent (e.g., core structure, or Y ₁₁ to Y ₁₃ rings, Y ₁₄ to Y ₁₆ It may be in the form of a condensed, fused, cross-linked, or spirocyclic bond.

For example, the A ring may be selected from the group consisting of a monocyclic or polycyclic alicyclic ring, a monocyclic or polycyclic heteroalicyclic ring, a monocyclic or polycyclic aromatic ring, and a monocyclic or polycyclic heteroaromatic ring. .

Y ₁ to Y ₁₆ are each independently C(R ₆ ) or N. Here, a plurality of R ₆ may be the same or different from each other, and may form a ring by combining with another adjacent R ₆ .

As a preferred example of the present invention, the polycyclic condensed ring represented by Formula 3 may be selected from the structures below.

In the above substituents,

* is a site connected to R ₁ and R ₂ of Formula 1 or 2, respectively,

X is selected from the group consisting of O, S, Se, N(Ar ₁ ), C(Ar ₂ )(Ar ₃ ), and Si(Ar ₄ )(Ar ₅ ).

Ar ₁ to Ar ₅ are the same or different from each other, and are each independently selected from the group consisting of an aryl group with 6 to 30 carbon atoms and a heteroaryl group with 5 to 30 nuclear atoms.

In the present invention, Ar ₁ to Ar ₅ is preferably each independently an aryl group of C ₆ to C ₆₀ , a heteroaryl group of 5 to 60 nuclear atoms, and an arylamine group of C ₆ to C ₆₀ .

When R is plural, the plurality of R's are the same or different from each other, and each independently represents hydrogen, deuterium, halogen, cyano group, nitrile group, sulfonyl group, alkyl group of 1 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, and heteroaryl groups having 5 to 30 nuclear atoms.

In the present invention, R is preferably each independently selected from the group consisting of hydrogen, an alkyl group of C ₁ to C ₄₀ , an aryl group of C ₆ to C ₆₀ , and a heteroaryl group of 5 to 60 nuclear atoms.

In Ar ₁ to Ar ₅ and R, the alkyl group, aryl group, and heteroaryl group are each independently deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ to C ₆₀ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C At least one substituent selected from the group consisting of an aryl boron group of ₆ to C ₆₀ , an arylphosphine group of C ₆ to C ₆₀ , an arylphosphine oxide group of C ₆ to C ₆₀ , and an arylamine group of C ₆ to C ₆₀ can be replaced.

R ₃ to R ₆ are the same or different from each other, and are each independently hydrogen, deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ ~C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ to C ₄₀ arylamine group, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to It may be selected from the group consisting of a C ₄₀ aryl boron group, a C ₆ to C ₄₀ arylphosphine group, a C ₆ to C ₄₀ arylphosphine oxide group, and a C ₆ to C ₄₀ arylsilyl group.

In the present invention, R ₃ to R ₆ are each independently hydrogen, deuterium, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, and C ₆ ~ C It is preferably selected from the group consisting of ₄₀ arylamine groups.

a to c are each independently integers from 0 to 3. Here, when a to c are each independently 0, R ₃ to R ₆ are each independently hydrogen, and when a to c are 1 to 3, R ₃ to R ₆ may have the above-mentioned substituents excluding hydrogen. .

In R ₁ to R ₆ an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, aryl The boron group, arylphosphine group, arylphosphine oxide group, and arylamine group each independently contain deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ to C ₆₀ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphine group, C ₆ to C ₆₀ arylphosphine oxide group, and C ₆ to C ₆₀ arylamine group. In this case, when substituted with a plurality of substituents, they may be the same or different from each other.

According to a preferred example of the present invention, at least one of R ₃ to R ₆ may be a substituent represented by the following formula (4). Preferably, at least one of R ₃ to R ₅ may be a substituent with electron-withdrawing group (EWG) properties.

In Formula 4, * refers to a portion bonded to Formula 1 or Formula 2.

L ₁ may be a linker of a typical divalent group known in the art. For example, L ₁ may be a single bond, or may be selected from the group consisting of an arylene group having C ₆ to C ₁₈ and a heteroarylene group having 5 to 18 nuclear atoms.

More specific examples of L ₁ include phenylene group, biphenylene group, naphthylene group, anthracenylene group, indenylene group, pyrantrenylene group, carbazolylene group, thiophenylene group, indolylene group, purinylene group, quinine. There are nolinylene group, pyrrolylene group, imidazolylene group, oxazolylene group, thiazolilene group, triazonylene group, pyridinylene group, pyrimidinylene group, etc.

In the present invention, L ₁ is preferably a single bond, a phenylene group, a biphenylene group, or a carbazolyl group.

Z ₁ to Z ₅ are the same or different from each other and are each independently N or C(R ₁₀ ), however, it is preferable that at least one of Z ₁ to Z ₅ is N.

In addition, when C(R ₁₀ ) is plural, the plurality of R ₁₀ are the same or different from each other, and are each independently hydrogen, deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ to C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ A group consisting of a C ₄₀ alkyl boron group, a C ₆ ~ C ₄₀ aryl boron group, a C ₆ ~ C ₄₀ arylphosphine group, a C ₆ ~ C ₄₀ arylphosphine oxide group, and a C ₆ ~ C ₄₀ arylsilyl group or R ₁₀ may be combined with an adjacent group (eg, L ₁ , another adjacent R ₁₀ ) to form a condensed ring.

In the present invention, R ₁₀ is preferably selected from the group consisting of hydrogen, an alkyl group of C ₁ to C ₄₀ , an aryl group of C ₆ to C ₄₀ , and a heteroaryl group of 5 to 40 nuclear atoms.

The arylene group and heteroarylene group of L ₁ ; The _alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group, Arylphosphine group, arylphosphine oxide group, and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₄₀ Arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ may be substituted with one or more substituents selected from the group consisting of aryl boron group, C ₆ ~ C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ arylphosphine oxide group, and C ₆ ~ C ₄₀ arylsilyl group, At this time, when the substituents are plural, they may be the same or different from each other.

The substituent represented by Formula 4 may be further specified as any one of the substituent groups represented by the following Formulas A-1 to A-15.

In A-1 to A-15 above,

L ₁ and R ₁₀ are each as defined in Formula 4 above,

n is an integer from 0 to 4, and when n is 0, R ₁₁ is hydrogen, and when n is an integer from 1 to 4, R ₁₁ is deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, C ₆ to C ₄₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₄₀ arylamine group, C ₁ to C ₄₀ alkyl Silyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ arylphosphine oxide group and C ₆ ~ C ₄₀ may be selected from the group consisting of an arylsilyl group, or may be combined with an adjacent group to form a condensed ring,

The _alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group, Arylphosphine group, arylphosphine oxide group, and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, sulfonyl group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₄₀ Arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group with 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ may be substituted with one or more substituents selected from the group consisting of aryl boron group, C ₆ ~ C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ arylphosphine oxide group, and C ₆ ~ C ₄₀ arylsilyl group, At this time, when the substituents are plural, they may be the same or different from each other.

The compound represented by Formula 1 or Formula 2 of the present invention described above may be further specified as a compound represented by any one of the compounds exemplified below, for example, J-1 to J-96. However, the compounds represented by Formula 1 or Formula 2 of the present invention are not limited to those exemplified below.

In the present invention, “alkyl” refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc., but are not limited thereto.

In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include vinyl, allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof include ethynyl, 2-propynyl, etc., but are not limited thereto.

In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms, either a single ring or a combination of two or more rings. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may also be included. Examples of such aryl include phenyl, naphthyl, phenanthryl, anthryl, etc., but are not limited thereto.

In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At this time, at least one carbon, preferably 1 to 3 carbons, of the ring is replaced with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply pendant or condensed with each other may be included, and a condensed form with an aryl group may also be included. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, phenoxathienyl, indolizinyl, and indolyl ( Polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, etc., but are not limited thereto.

In the present invention, “aryloxy” is a monovalent substituent represented by RO-, where R refers to aryl having 5 to 40 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy, etc., but are not limited thereto.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, where R' refers to alkyl having 1 to 40 carbon atoms and has a linear, branched, or cyclic structure. may include. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, and pentoxy.

In the present invention, “arylamine” refers to an amine substituted with aryl having 6 to 40 carbon atoms.

In the present invention, “cycloalkyl” refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

In the present invention, “heterocycloalkyl” refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S Or it is substituted with a hetero atom such as Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

In the present invention, “alkylsilyl” refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” refers to silyl substituted with aryl having 5 to 40 carbon atoms.

In the present invention, “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

<Organic electroluminescent device>

Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) containing the compound represented by Formula 1 or 2 according to the above-described present invention.

More specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, and at least one of the one or more organic material layers includes compounds represented by Formula 1 or 2 above. At this time, the above compounds may be used alone, or two or more may be used in combination.

The one or more organic layers may be any one or more of a hole injection layer, a hole transport layer, an auxiliary light emitting layer, a light emitting layer, an electron transport layer, and an electron injection layer, and at least one of these organic layers includes a compound represented by Formula 1 or 2. can do. Specifically, the organic material layer containing the compound of Formula 1 or 2 is preferably a light emitting layer, an electron transport layer, or a hole transport layer.

The light-emitting layer of the organic electroluminescent device of the present invention may include a host material, and in this case, the host material may include the compound of Formula 1 or 2 above. Additionally, the light-emitting layer of the organic electroluminescent device of the present invention may include a compound other than the compound of Formula 1 or 2 as a host.

When the compound represented by Formula 1 or 2 is included as a light-emitting layer material of an organic electroluminescent device, preferably a blue, green, or red phosphorescent host material, the binding force between holes and electrons in the light-emitting layer increases, so that the organic electroluminescent device Efficiency (luminous efficiency and power efficiency), lifespan, brightness, and driving voltage can be improved. Specifically, the compound represented by Formula 1 or 2 is preferably included in an organic electroluminescent device as a green and/or red phosphorescent host, fluorescent host, or dopant material. In particular, the compound represented by Formula 1 or 2 of the present invention is preferably a phosphorescent host, fluorescent host, or dopant material of the light-emitting layer, and more preferably is a red phosphorescent host of the light-emitting layer.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, an auxiliary light emitting layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked. At this time, one or more of the hole injection layer, hole transport layer, auxiliary light emitting layer, light emitting layer, electron transport layer, and electron injection layer may include a compound represented by Formula 1 or 2, and preferably a hole transport layer or an electron blocking layer. , the light emitting auxiliary layer may include a compound represented by Formula 1 or 2 above. Meanwhile, an electron injection layer may be additionally laminated on the electron transport layer.

The structure of the organic electroluminescent device of the present invention may be one in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.

The organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer contains a compound represented by Formula 1 or 2. there is.

The organic material layer may be formed by vacuum deposition or solution application. Examples of the solution application method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The substrate used in manufacturing the organic electroluminescent device of the present invention is not particularly limited, but silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, etc. can be used.

In addition, the anode material includes 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); Combinations of metals and oxides such as ZnO:Al or SnO2:Sb; Conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, or polyaniline; and carbon black, but are not limited thereto.

Additionally, the cathode material includes metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; and multilayer structure materials such as LiF/Al or LiO2/Al, etc., but are not limited thereto.

Additionally, the hole injection layer, hole transport layer, electron injection layer, and electron transport layer are not particularly limited, and common materials known in the art can be used.

Hereinafter, the present invention will be described in detail through examples. However, the following examples only illustrate the present invention, and the present invention is not limited by the following examples.

< Preparation example >

[Preparation Example 1] Synthesis of A-1

<Step 1> Synthesis of 4-(2-bromo-4-chlorophenyl)-9,9-diphenyl-9H-fluorene

(9,9-diphenyl-9H-fluoren-4-yl)boronic acid (3.62 g, 10 mmol), 2-bromo-4-chloro-1-iodobenzene (3.17 g, 10 mmol), and Pd(PPh) under a nitrogen stream. ₃ ) Mix ₄ (0.57 g, 5 mol%), K ₂ CO ₃ (2.76 g, 20 mmol), Toluene/Ethanol/H ₂ O (100 ml/75 ml/50 ml) and then brew at 80°C for 12 hours. It was stirred for a while. After completion of the reaction, extraction was performed with methylene chloride, then MgSO ₄ was added and filtered. After removing the solvent from the obtained organic layer, the target compound, 4-(2-bromo-4-chlorophenyl)-9,9-diphenyl-9H-fluorene (3.60 g, yield 71%), was obtained using column chromatography.

¹ H-NMR: δ 7.10~7.28 (m, 11H), 7.35~7.60 (m, 6H), 7.77 (d, 1H), 7.90 (m, 2H)

<Step 2> Synthesis of A-1

4-(2-bromo-4-chlorophenyl)-9,9-diphenyl-9H-fluorene (5.07 g, 10 mmol) and Pd(PPh ₃ ) ₂ Cl ₂ synthesized in Preparation Example 1 <Step 1> under a nitrogen atmosphere. (0.35 g, 5 mol%), DBU (7.61 g, 50 mmol), and DMF (100 ml) were mixed and stirred at 150°C for 24 hours. After completion of the reaction, DMF was removed, extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, the target compound A-1 (2.13 g, yield 50%) was obtained using column chromatography.

¹ H-NMR: δ 7.10~7.26 (m, 10H), 7.62 (t, 2H), 7.78 (m, 3H), 8.10 (m, 3H), 8.94 (s, 1H)

[Preparation Example 2] Synthesis of A-2

Except that 9,9'-spirobi[fluoren]-4-ylboronic acid (3.60 g, 10 mmol) was used instead of (9,9-diphenyl-9H-fluoren-4-yl)boronic acid as the reactant in <Step 1>. Then, the same process as [Preparation Example 1] was performed to obtain the target compound A-2 (2.08 g, yield 49%).

¹ H-NMR: δ 7.28~7.38 (m, 4H), 7.60 (m, 4H), 7.78~7.90 (m, 5H), 8.07 (m, 3H), 8.99 (s, 1H)

[Preparation Example 3] Synthesis of A-3

As a reactant in <Step 1>, (9,9-dimethyl-9H-fluoren-4-yl)boronic acid (2.38 g, 10 mmol) was used instead of (9,9-diphenyl-9H-fluoren-4-yl)boronic acid. The same process as [Preparation Example 1] was performed, except that 3-bromo-5-chloro-2-iodopyridine (3.18 g, 10 mmol) was used instead of 2-bromo-4-chloro-1-iodobenzene. Thus, the target compound A-3 (1.45 g, yield 48%) was obtained.

¹ H-NMR: δ 1.95 (s, 6H), 7.62 (t, 2H), 7.78 (d, 2H), 8.03 (m, 3H), 8.81 (s, 1H)

[Preparation Example 4] Synthesis of A-4

<Step 1> Synthesis of 4-(3'-chloro-[1,1'-biphenyl]-2-yl)-4H-cyclopenta[def]phenanthren-4-ol

2-bromo-3'-chloro-1,1'-biphenyl (2.67 g, 10 mmol) was dissolved in 25 mL of THF and cooled to -78°C. 2.5M n-BuLi (4 mL, 10 mmol) was added dropwise here, stirred for 2 hours, and then 4H-cyclopenta[def]phenanthren-4-one (2.04 g, 10 mmol) was dissolved in 10 mL of THF and added dropwise. did. After the dropwise addition, the temperature was gradually raised to room temperature, stirred for 12 hours, and then extracted using ethyl acetate and water. The organic layer was collected separately and distilled under reduced pressure to remove the solvent and volatile substances, and then proceeded with the next reaction without additional purification.

<Step 2> Synthesis of A-4

4-(3'-chloro-[1,1'-biphenyl]-2-yl)-4H-cyclopenta[def]phenanthren-4-ol (3.92 g, 10 mmol) synthesized in <Step 1> was added to the reactor. Then, 40 mL of acetic acid and 40 mL of 36% HCl were added, and the mixture was refluxed and stirred for 12 hours. After completing the reaction, the solution was cooled and the solid was filtered. The filtered solid was washed with methanol, and the target compound, A-4 (1.76 g, yield 47%), was obtained from the remaining solid using column chromatography.

¹ H-NMR: δ 7.29 (m, 2H) 7.38 (t, 1H), 7.49~7.62 (m, 4H), 7.80~7.92 (m, 8H)

[Preparation Example 5] Synthesis of A-5

As a reactant in <Step 1>, 2-bromo-N-(2-bromophenyl)-N-phenylaniline (4.03 g, 10 mmol) was used instead of 2-bromo-3'-chloro-1,1'-biphenyl, and 4H- The same procedure as [Preparation Example 4] was performed except that 4H-cyclopenta[def]triphenylen-4-one (2.54 g, 10 mmol) was used instead of cyclopenta[def]phenanthren-4-one, and the target compound A was obtained. -5 (2.57 g, yield 46%) was obtained.

¹ H-NMR: δ 6.80~7.20 (m, 11H), 7.56~7.67 (m, 5H), 7.78(d, 2H), 8.07 (d, 2H), 8.67 (d, 2H)

[Preparation Example 6] Synthesis of A-6

As a reactant in <Step 1>, 1-iodotriphenylene (3.54 g, 10 mmol) is used instead of 2-bromo-3'-chloro-1,1'-biphenyl, and 2- instead of 4H-cyclopenta[def]phenanthren-4-one is used. Except for using bromo-9H-fluoren-9-one (2.59 g, 10 mmol), the same process as [Preparation Example 4] was performed to obtain the target compound A-6 (2.11 g, yield 45%). .

¹ H-NMR: δ 7.28 (t, 1H), 7.38 (t, 1H), 7.55~7.77 (m, 10H), 7.90 (d, 1H), 8.07 (d, 2H), 8.66 (d, 2H)

[Preparation Example 7] Synthesis of A-7

As the reactant in <Step 1>, 1-iodotriphenylene (3.54 g, 10 mmol) is used instead of 2-bromo-3'-chloro-1,1'-biphenyl, and 2- instead of 4H-cyclopenta[def]phenanthren-4-one is used. Except for using bromo-4H-cyclopenta[def]phenanthren-4-one (2.83 g, 10 mmol), the same process as [Preparation Example 4] was performed to obtain the target compound A-7 (2.17 g, yield 44 %) was obtained.

¹ H-NMR: δ 7.62~7.65 (m, 5H), 7.78~7.80 (m, 4H), 7.93 (m, 3H), 8.07 (d, 2H), 8.19 (s, 1H), 8.67 (d, 2H) )

[Preparation Example 8] Synthesis of A-8

As a reactant in <Step 1>, 1,4-dibromo-7-(tert-butyl)triphenylene (4.42 g, 10 mmol) was used instead of 2-bromo-3'-chloro-1,1'-biphenyl, and 4H-cyclopenta The same process as [Preparation Example 4] was performed except that 7H-benzo[de]anthracen-7-one (2.30 g, 10 mmol) was used instead of [def]phenanthren-4-one, and the target compound A- was obtained. 8 (2.47 g, yield 43%) was obtained.

¹ H-NMR: δ 1.49 (s, 9H), 6.86 (d, 1H), 7.38 (m, 4H), 7.67~7.74 (m, 5H), 7.91(d, 1H), 8.00~8.06 (m, 4H) ), 8.15 (s, 1H), 8.50 (d, 1H), 8.84 (d, 1H)

[Preparation Example 9] Synthesis of A-9

As the reactant in <Step 1>, 4-(4-bromotriphenylen-1-yl)-2,6-diphenylpyrimidine (5.37 g, 10 mmol) was used instead of 2-bromo-3'-chloro-1,1'-biphenyl. The purpose was the same as [Preparation Example 4], except that 4-chloro-9H-thioxanthen-9-one (2.46 g, 10 mmol) was used instead of 4H-cyclopenta[def]phenanthren-4-one. Compound A-9 (2.88 g, yield 42%) was obtained.

¹ H-NMR: δ 6.88 (d, 1H), 7.03~7.06 (m, 3H), 7.33 (t, 1H), 7.44~7.66 (m, 11H), 7.78 (d, 1H), 7.94 (m, 3H) ), 8.07 (d, 1H), 8.14 (d, 1H), 8.23~8.35 (m, 4H), 8.98 (d, 1H)

[Preparation Example 10] Synthesis of A-10

As the reactant in <Step 1>, 1,4-dibromotriphenylene (3.86 g, 10 mmol) is used instead of 2-bromo-3'-chloro-1,1'-biphenyl, and instead of 4H-cyclopenta[def]phenanthren-4-one Except for using 3-chloro-9H-fluoren-9-one (4.28 g, 20 mmol), the same process as [Preparation Example 4] was performed to obtain the target compound A-10 (2.54 g, yield 41%). got it

¹ H-NMR: δ 7.29~7.38 (m, 6H), 7.55~7.62 (m, 6H), 7.70~7.90 (m, 8H), 8.07 (d, 2H)

[Preparation Example 11] Synthesis of A-11

6-(2-bromophenyl)-5,12-diphenyl-5,12-dihydroindolo[3,2-a]carbazole instead of 2-bromo-3'-chloro-1,1'-biphenyl as the reactant in <Step 1> (5.63 g, 10 mmol), except that 5-chloro-9H-cyclopenta[lmn]phenanthridin-9-one (2.39 g, 10 mmol) is used instead of 4H-cyclopenta[def]phenanthren-4-one. performed the same process as [Preparation Example 4] to obtain the target compound A-11 (2.80 g, yield 40%).

¹ H-NMR: δ 7.16 (t, 2H), 7.35-7.82 (m, 21H), 7.94 (d, 2H), 8.24 (d, 1H), 8.55 (d, 2H)

[Preparation Example 12] Synthesis of A-12

<Step 1> Synthesis of 4,4,5,5-tetramethyl-2-(spiro[fluorene-9,9'-xanthen]-4-yl)-1,3,2-dioxaborolane

4-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2' under nitrogen stream. -bi(1,3,2-dioxaborolane) (2.53 g, 10 mmol), Pd(dppf)Cl ₂ (0.36 g, 5 mol%), KOAc (1.96 g, 20 mmol), 1,4-Dioxane (100 ml) were mixed and then stirred at 100°C for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, then MgSO ₄ was added and filtered. After removing the solvent from the obtained organic layer, the target compound, 4,4,5,5-tetramethyl-2-(spiro[fluorene-9,9'-xanthen]-4-yl)-1,3, 2-dioxaborolane (2.79 g, yield 61%) was obtained.

¹ H-NMR: δ 1.21 (s, 12H), 7.01~7.06 (m, 4H), 7.14~7.17 (m, 6H), 7.31 (m, 4H), 7.90 (d, 1H)

<Step 2> Synthesis of 9-chlorospiro[cyclopenta[def]triphenylene-4,9'-xanthene]

As a reactant in <Step 1>, instead of (9,9-diphenyl-9H-fluoren-4-yl)boronic acid, 4,4,5,5-tetramethyl-2-(spiro[fluorene-9,9'-) synthesized above was used. The target compound 9-chlorospiro[cyclopenta[def] was prepared in the same manner as in [Preparation Example 1], except for using ] triphenylene-4,9'-xanthene] (1.80 g, yield 41%) was obtained.

¹ H-NMR: δ 7.01 (t, 2H), 7.14~7.17 (m, 4H), 7.31 (t, 2H), 7.62 (t, 2H), 7.78 (m, 3H), 8.07 (m, 3H), 8.94 (s, 1H)

<Step 3> Synthesis of A-12

9-chlorospiro[cyclopenta[def]triphenylene-4,9'-xanthene] (4.40 g, 10 mmol), 4,4,4',4',5,5,5',5'-octamethyl- under nitrogen stream. 2,2'-bi(1,3,2-dioxaborolane) (2.53 g, 10 mmol), Pd(OAc) ₂ (0.11 g, 5 mol%), XPhos (0.47 g, 1 mmol), KOAc (1.96 g , 20 mmol) and 1,4-Dioxane (100 ml) were mixed and stirred at 100°C for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, then MgSO ₄ was added and filtered. After removing the solvent from the obtained organic layer, the target compound A-12 (2.39 g, yield 45%) was obtained using column chromatography.

¹ H-NMR: δ 1.20 (s, 12H), 7.01 (t, 2H), 7.14~7.17 (m, 4H), 7.31 (t, 2H), 7.62 (m, 3H), 7.78 (m, 2H), 8.07~8.11 (m, 3H), 8.76 (s, 1H)

[Preparation Example 13] Synthesis of A-13

<Step 1> Synthesis of 4'-bromospiro[benzofuro[3',2':6,7]indeno[1,2-b]pyridine-5,9'-fluorene]

The reactant in <Step 1> was 3-bromo-2-(dibenzo[b,d]furan-4-yl)pyridine (3.24 g, 10 mmol) instead of 2-bromo-3'-chloro-1,1'-biphenyl. The same process as [Preparation Example 4] was used, except that 4-bromo-9H-fluoren-9-one (2.59 g, 10 mmol) was used instead of 4H-cyclopenta[def]phenanthren-4-one. The target compound 4'-bromospiro[benzofuro[3',2':6,7]indeno[1,2-b]pyridine-5,9'-fluorene] (2.23 g, yield 46%) was obtained.

¹ H-NMR: δ 6.67 (t, 1H), 7.17~7.38 (m, 7H), 7.49~7.54 (m, 4H), 7.90~7.98 (m, 3H), 8.35 (d, 1H)

<Step 2> Synthesis of A-13

As the reactant in <Step 1>, replace 4-bromospiro[fluorene-9,9'-xanthene] with 4'-bromospiro[benzofuro[3',2':6,7]indeno[1,2-b]pyridine-5, 9'-fluorene] (4.86 g, 10 mmol) and instead of 2-bromo-4-chloro-1-iodobenzene in <Step 2>, use 2-bromo-1-chloro-3-iodobenzene (3.17 g, 10 mmol) Except for using, the same process as in [Preparation Example 12] was performed to obtain the target compound A-13 (2.85 g, yield 47%).

¹ H-NMR: δ 1.24 (s, 12H), 6.67 (t, 1H), 7.22 (d, 1H), 7.29~7.39 (m, 3H), 7.54-7.62 (m, 4H), 7.71 (d, 1H) ), 7.78 (m, 2H), 7.98 (m, 2H), 8.07 (m, 2H), 8.17 (d, 1H), 8.35 (d, 1H)

[Preparation Example 14] Synthesis of A-14

As the reactant in <Step 1>, 2,2'-dibromo-1,1'-biphenyl (3.12 g, 10 mmol) was used instead of 3-bromo-2-(dibenzo[b,d]furan-4-yl)pyridine. And, instead of 4-bromo-9H-fluoren-9-one, 2-chloro-10,10-dimethylanthracen-9(10H)-one (2.56 g, 10 mmol) was used, and 2-bromo was used as the reactant in <Step 2>. The same procedure as [Preparation Example 13] was performed except that 2-bromo-3-iodopyrazine (2.84 g, 10 mmol) was used instead of -1-chloro-3-iodobenzene, and the target compound A-14 (2.69 g) was obtained. , yield 48%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 1.69 (s, 6H), 7.20~7.30 (m, 7H), 7.62 (t, 2H), 7.78 (d, 2H), 8.01 (d, 2H), 8.74 (d, 2H)

< Synthesis example >

[Synthesis Example 1] Synthesis of J-1

A-1 (4.26 g, 10 mmol), 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) under nitrogen flow. -1,3,5-triazine (4.35 g, 10 mmol), Pd(OAc) ₂ (0.11 g, 5 mol%), Xphos (0.47 g, 2 mmol), Cs ₂ CO ₃ (6.51 g, 20 mmol) , Toluene/EtOH/H ₂ O (80 ml/40 ml/20 ml) were mixed and stirred at 110°C for 6 hours. After completion of the reaction, the extract was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, the target compound, J-1 (3.42 g, yield 49%), was obtained using column chromatography.

[LCMS] : 699

[Synthesis Example 2] Synthesis of J-2

Use A-2 (4.24 g, 10.0 mmol) instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) instead of phenyl)-1,3,5-triazine, 2,4-diphenyl-6-(3'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1 The target compound, J-2 ( 3.86 g, yield 50%) was obtained.

[LCMS] : 773

[Synthesis Example 3] Synthesis of J-3

A-3 (3.03 g, 10.0 mmol) was used instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) instead of phenyl)-1,3,5-triazine, 2,4-diphenyl-6-(3''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[ The same process as Synthesis Example 1 was performed, except for using 1,1':3',1''-terphenyl]-3-yl)-1,3,5-triazine (5.87 g, 10.0 mmol). The target compound, J-3 (3.71 g, yield 51%) was obtained.

[LCMS] : 728

[Synthesis Example 4] Synthesis of J-4

Use A-4 (3.74 g, 10.0 mmol) instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl )phenyl)-1,3,5-triazine instead of 2-([1,1'-biphenyl]-4-yl)-4-(4-fluorophenyl)-6-(4-(4,4,5,5 The target compound, J-4 (3.85% g, yield 52%) was obtained.

[LCMS] : 740

[Synthesis Example 5] Synthesis of J-5

A-5 (5.60 g, 10 mmol), 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) under nitrogen flow. pyrimidine (4.34 g, 10.0 mmol), Pd(PPh ₃ ) ₄ (0.57 g, 5 mol%), K ₂ CO ₃ (2.76 g, 20 mmol), Toluene/Ethanol/H ₂ O (100 ml/75 ml/ 50 ml) were mixed and then stirred at 80°C for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, then MgSO ₄ was added and filtered. After removing the solvent from the obtained organic layer, the target compound, J-5 (4.17 g, yield 53%), was obtained using column chromatography.

[LCMS] : 787

[Synthesis Example 6] Synthesis of J-6

Use A-6 (4.69 g, 10.0 mmol) instead of A-5 and 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl )phenyl)pyrimidine instead of 4-([1,1'-biphenyl]-4-yl)-2-phenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- Except for using 2-yl)phenyl)pyrimidine (5.10 g, 10.0 mmol), the same procedure as in Synthesis Example 5 was performed to obtain the target compound, J-6 (4.17 g, yield 54%).

[LCMS] : 772

[Synthesis Example 7] Synthesis of J-7

Use A-7 (4.93 g, 10.0 mmol) instead of A-5 and 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl The target compound, J-7 ( 3.94 g, yield 55%) was obtained.

[LCMS] : 716

[Synthesis Example 8] Synthesis of J-8

Under nitrogen flow, A-8 (5.75 g, 10 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (4.08 g, 10 mmol), Pd(OAc) ₂ (0.11 g, 5 mol% ), P(t-Bu) ₃ (0.20 g, 1 mmol), NaO(t-Bu) (1.92 g, 20 mmol), and Toluene (200 ml) were mixed and stirred at 110°C for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, then MgSO ₄ was added and filtered. After removing the solvent from the obtained organic layer, the target compound, J-8 (5.05 g, yield 56%) was obtained using column chromatography.

[LCMS]: 903

[Synthesis Example 9] Synthesis of J-9

Use A-9 (6.87 g, 10.0 mmol) instead of A-8 and N-([1,1'-biphenyl]-4-yl) instead of 9-phenyl-9H,9'H-3,3'-bicarbazole. The target compound, J-9 (5.77 g, yield 57 %) was obtained.

[LCMS] : 1012

[Synthesis Example 10] Synthesis of J-10

A-10 (6.21 g, 10.0 mmol) was used instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) The same process as Synthesis Example 1 was performed, except that (4-(diphenylamino)phenyl)boronic acid (5.78 g, 20.0 mmol) was used instead of phenyl)-1,3,5-triazine, and the target compound, J -10 (6.02 g, yield 58%) was obtained.

[LCMS]: 1038

[Synthesis Example 11] Synthesis of J-11

A-11 (7.06 g, 10.0 mmol) was used instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) The same process as Synthesis Example 1 was performed, except that (9-phenyl-9H-carbazol-3-yl)boronic acid (2.87 g, 10.0 mmol) was used instead of phenyl)-1,3,5-triazine. The target compound, J-11 (5.38 g, yield 59%) was obtained.

[LCMS]: 913

[Synthesis Example 12] Synthesis of J-12

A-12 (5.32 g, 10.0 mmol) was used instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl )Same process as Synthesis Example 1, except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.67 g, 10.0 mmol) was used instead of phenyl)-1,3,5-triazine. was performed to obtain the target compound, J-12 (3.82 g, yield 60%).

[LCMS] : 637

[Synthesis Example 13] Synthesis of J-13

A-13 (6.07 g, 10.0 mmol) was used instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) The same process as Synthesis Example 1 was performed, except that 2-chloro-4-phenylquinazoline (2.40 g, 10.0 mmol) was used instead of phenyl)-1,3,5-triazine, and the target compound, J-13 ( 4.18 g, yield 61%) was obtained.

[LCMS] : 685

[Synthesis Example 14] Synthesis of J-14

A-14 (5.60 g, 10.0 mmol) was used instead of A-1 and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) The same process as Synthesis Example 1 was performed except that 2-chloro-4-phenylbenzo[h]quinazoline (2.90 g, 10.0 mmol) was used instead of phenyl)-1,3,5-triazine to produce the target compound. J-14 (4.27 g, yield 62%) was obtained.

[LCMS] : 688

[Examples 1 to 14] Fabrication of organic EL device

The compounds synthesized in Synthesis Examples 1 to 14 were purified to high purity by sublimation using a commonly known method, and then a green organic EL device was manufactured according to the process below.

First, a glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, the substrate is ultrasonic cleaned with solvents such as isopropyl alcohol, acetone, and methanol, dried, and then transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech). Then, the substrate is cleaned using UV for 5 minutes and then vacuum evaporated. The substrate was transferred to .

On the ITO transparent electrode prepared in this way, m-MTDATA (60 nm)/TCTA (80 nm)/90% host compound of Table 1 + 10% Ir(ppy) ₃ (300 nm)/BCP (10 nm)/Alq ₃ (30%) An organic EL device was manufactured by stacking in the following order: nm)/LiF (1 nm)/Al (200 nm).

The structures of m-MTDATA, TCTA, Ir(ppy) ₃ , CBP and BCP are as follows.

[Comparative Example 1] Fabrication of organic EL device

An organic EL device was manufactured in the same process as Example 1, except that CBP was used instead of Compound J-1 as the light-emitting host material when forming the light-emitting layer.

[Evaluation example]

The driving voltage, current efficiency, and luminescence peak at a current density of 10 mA/cm2 were measured for each organic EL device manufactured in Examples 1-14 and Comparative Example 1, and the results are shown in Table 1 below.

Sample host driving voltage EL peak Current efficiency (V) (nm) (cd/A) Example 1 J-1 6.81 518 39.7 Example 2 J-2 6.68 518 38.9 Example 3 J-3 6.66 518 41.3 Example 4 J-4 6.7 517 41.3 Example 5 J-5 6.7 515 43.1 Example 6 J-6 6.51 518 43.5 Example 7 J-7 6.77 518 41.4 Example 8 J-8 6.66 518 42.5 Example 9 J-9 6.81 517 41.3 Example 10 J-10 6.66 515 41.3 Example 11 J-11 6.81 518 41.2 Example 12 J-12 6.68 518 41.3 Example 13 J-13 6.66 518 39.7 Example 14 J-14 6.81 517 42 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, the green organic EL devices of Examples 1-14 using the compounds (J-1 to J-14) according to the present invention as the emitting layer of the green organic EL device are compared to those using conventional CBP. Compared to the green organic EL device of Example 1, it was found to exhibit excellent performance in terms of efficiency and driving voltage.

[Examples 15 to 28] Fabrication of blue organic electroluminescent device

The compounds (J-1 to J-14) synthesized in the synthesis examples were purified by sublimation to high purity using a commonly known method, and then a blue organic electroluminescent device was manufactured according to the following process.

First, a glass substrate coated with a 1500 Å thin film of ITO (indium tin oxide) was washed with distilled water ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, and methanol, drying, transferring to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then cleaning the substrate for 5 minutes using UV. and transferred the substrate to a vacuum evaporator.

On the ITO transparent electrode prepared as above, DS-205 (Doosan Electronics Co., Ltd., 80 nm)/NPB (15 nm)/ADN + 5% DS-405 (Doosan Electronics Co., Ltd., 30nm)/ Compound J-1~14 (5 An organic electroluminescent device was manufactured by stacking in the following order: nm)/Alq ₃ (25 nm)/LiF (1 nm)/Al (200 nm).

[Comparative Example 2] Preparation of blue organic electroluminescent device

A blue organic electroluminescent device was produced in the same manner as Example 15, except that Compound J-1 was not used as the electron transport auxiliary layer material and Alq ₃ , the electron transport layer material, was deposited at 30 nm instead of 25 nm. Produced.

[Evaluation Example 2]

For the organic electroluminescent devices manufactured in Examples 15 to 28 and Comparative Example 2, the driving voltage, emission wavelength, and current efficiency were measured at a current density of 10 mA/cm2, and the results are shown in Table 2 below.

Sample Electron transport auxiliary layer Driving voltage (V) Emission peak (nm) Current efficiency (cd/A) Example 15 J-1 4.0 458 8.1 Example 16 J-2 4.1 455 8.2 Example 17 J-3 3.9 457 8.0 Example 18 J-4 4.5 455 8.6 Example 19 J-5 3.4 452 8.4 Example 20 J-6 4.5 457 7.9 Example 21 J-7 3.7 457 7.8 Example 22 J-8 3.8 457 8.4 Example 23 J-9 4.6 456 6.6 Example 24 J-10 3.8 453 9.0 Example 25 J-11 3.9 454 8.1 Example 26 J-12 4.7 456 7.7 Example 27 J-13 4.1 453 6.8 Example 28 J-14 4.6 452 8.7 Comparative Example 2 - 4.8 458 6.0

As shown in Table 2, the blue organic electroluminescent device of Examples 15 to 28 using the compound of the present invention in the electron transport auxiliary layer has a higher density than the blue organic electroluminescent device of Comparative Example 2 without the electron transport auxiliary layer. It was found to exhibit excellent performance in terms of current efficiency, luminescence peak, and driving voltage.

Claims (7)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are the same or different from each other, and are each independently an alkyl group of C ₁ to C ₄₀ , an aryl group of C ₆ to C ₄₀ , or a polycyclic condensed ring,
Y ₁ to Y ₁₀ are each independently CR ₆ or N, provided that when R ₁ and R ₂ are an alkyl group, at least one of Y ₁ to Y ₁₀ includes N,
Here, a plurality of R ₆ are the same or different from each other and can form a ring by combining with other adjacent R ₆ ,
R ₆ that does not form a ring is each independently selected from the group consisting of hydrogen, an alkyl group of C ₁ to C ₄₀ , an aryl group of C ₆ to C ₄₀ , and a heteroaryl group of 5 to 40 nuclear atoms,
R ₃ is selected from the group consisting of hydrogen, deuterium, C ₆ to C ₄₀ aryl group, heteroaryl group with 5 to 40 nuclear atoms, and C ₆ to C ₄₀ arylamine group,
a is 0 or 1,
The alkyl group, aryl group, heteroaryl group, and arylamine group in R ₃ and R ₆ are each independently a group consisting of deuterium, halogen, an aryl group of C ₆ to C ₆₀ , and a heteroaryl group of 5 to 60 nuclear atoms. may be substituted with one or more types selected from, and in this case, when substituted with a plurality of substituents, they are the same or different from each other,
The polycyclic condensed ring in R ₁ and R ₂ is represented by any of the following structural formulas,

In the above structural formula,
* is a site connected to R ₁ and R ₂ of Formula 1, respectively,
X is selected from the group consisting of O, S, N(Ar ₁ ), and C(Ar ₂ )(Ar ₃ ),
Ar ₁ to Ar ₃ are the same or different from each other, and are each independently selected from the group consisting of an alkyl group having 1 carbon atom and an aryl group having 6 carbon atoms,
A plurality of R's are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, an aryl group with 6 to 30 carbon atoms, a heteroaryl group with 5 to 30 nuclear atoms, and an arylamine group with C ₆ to C ₄₀ . And
In R, the aryl group, heteroaryl group, and arylamine group may each independently be substituted with one or more substituents selected from the group consisting of deuterium, halogen, an aryl group with 6 to 12 carbon atoms, and a heteroaryl group with 6 nuclear atoms, ,
However, the polycyclic condensed ring , and when R is hydrogen, R ₃ is a substituent represented by Formula 4,
[Formula 4]

In Formula 4 above,
* refers to the portion bonded to Formula 1 above,
L ₁ is a single bond or selected from the group consisting of an arylene group of C ₆ to C ₁₈ and a heteroarylene group of 5 to 18 nuclear atoms,
Z ₁ to Z ₅ are the same or different from each other and are each independently N or C(R ₁₀ ), provided that at least one of Z ₁ to Z ₅ is N,
When R ₁₀ is plural, the plurality of R ₁₀ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, and an aryl group of C ₆ to C ₁₂ . A compound represented by the following formula (2):
[Formula 2]

In Formula 2,
Y ₁ to Y ₈ are each independently CR ₆ or N,
Here, a plurality of R ₆ is each independently hydrogen,
R ₃ is selected from the group consisting of hydrogen, deuterium, an aryl group of C ₆ to C ₄₀ , and a heteroaryl group of 5 to 40 nuclear atoms,
a is 0 or 1,
The aryl group and heteroaryl group in R ₃ may each independently be substituted with one or more selected from the group consisting of deuterium, halogen, C ₆ to C ₁₈ aryl group, and heteroaryl group having 5 to 13 nuclear atoms; , In this case, when substituted with multiple substituents, they are the same or different from each other,
R ₁ and R ₂ are polycyclic condensed rings represented by any of the structural formulas below,

In the above structural formula,
* is a site connected to R ₁ and R ₂ of Formula 2, respectively,
X is N(Ar ₁ ),
Ar ₁ is each independently an aryl group having 6 carbon atoms,
A plurality of R is each independently selected from the group consisting of hydrogen, deuterium, and an aryl group having 6 carbon atoms,
The aryl groups in R may each independently be substituted with one or more substituents selected from the group consisting of deuterium, halogen, an aryl group with 6 to 12 carbon atoms, and a heteroaryl group with 6 nuclear atoms. According to paragraph 1,
When R ₁ and R ₂ are not condensed rings, at least one of Y ₁ to Y ₁₀ is N. According to claim 1 or 2,
A compound characterized in that at least one of R ₃ and R ₆ of Formula 1, or R ₃ of Formula 2 is a substituent represented by Formula 4:
[Formula 4]

In Formula 4 above,
* refers to a portion bonded to Formula 1 or Formula 2,
L ₁ is a single bond or selected from the group consisting of an arylene group of C ₆ to C ₁₈ and a heteroarylene group of 5 to 18 nuclear atoms,
Z ₁ to Z ₅ are the same or different from each other and are each independently N or C(R ₁₀ ), provided that at least one of Z ₁ to Z ₅ is N,
When R ₁₀ is plural, the plurality of R ₁₀ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, and an aryl group of C ₆ to C ₁₂ . According to paragraph 4,
A compound characterized in that the substituent represented by Formula 4 is any one of the substituent group represented by the following Formulas A-1 to A-9.

In A-1 to A-9 above,
L ₁ and R ₁₀ are as defined in clause 4. An organic electroluminescent device comprising an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers includes the compound according to claim 1 or 2. According to clause 6,
An organic electroluminescent device, wherein the organic material layer containing the compound is selected from the group consisting of a light-emitting layer, an electron injection layer, a light-emitting auxiliary layer, and a lifespan improvement layer.