KR102587380B1 - Organic compounds and organic electro luminescence device comprising the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device containing the same. The compound according to the present invention is used as a phosphorescent host material of an organic material layer, preferably a light-emitting layer, of an organic electroluminescent device, thereby increasing the luminous efficiency of the organic electroluminescent device, Driving voltage, lifespan, etc. can be improved.

Description

Organic compounds and organic electroluminescent devices containing the same {ORGANIC COMPOUNDS AND ORGANIC ELECTRO LUMINESCENCE DEVICE COMPRISING THE SAME}

The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescent device and an organic electroluminescent device containing 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.

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In order to solve the above problems, the present invention aims to provide a new compound that can improve the efficiency, lifespan, and stability of an organic electroluminescent device and an organic electroluminescent device using the compound.

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

[Formula 1]

In Formula 1,

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, an arylene group of C ₆ to C ₁₈ and a heteroarylene group of 5 to 18 nuclear atoms;

Ar ₁ and Ar ₂ are each independently a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, and 3 to 40 nuclear atoms. Heterocycloalkyl group, C ₆ ~ 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 ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ is selected from the group consisting of a mono or diarylphosphinyl group and a C ₆ to C ₆₀ arylamine group;

a is an integer from 0 to 3;

b is an integer from 0 to 4;

R ₁ and R ₂ are each independently selected from deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₃ to 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 to C ₄₀ alkyloxy group, C ₆ to C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ is selected from the group consisting of an arylphosphine group, a C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and a C ₆ ~ C ₆₀ arylamine group, and when each of R ₁ and R ₂ is plural, they are the same or different from each other and;

R ₃ and R ₄ are each independently selected from the group consisting of an alkyl group having C ₁ to C ₄₀ , an aryl group having C ₆ to C ₆₀ , and a heteroaryl group having 5 to 60 nuclear atoms;

The arylene group and heteroarylene group of L ₁ and L ₂ , the alkyl group, aryl group and heteroaryl group of Ar ₁ , Ar ₂ and R ₁ to R ₄ , and the Ar ₁ , Ar ₂ , R ₁ and R ₂ Alkenyl group, alkynyl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group, mono or diaryl phosphinyl group and aryl The silyl group is each independently deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₆ to C ₆₀ aryl group, Heteroaryl group with 5 to 60 nuclear atoms, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ arylamine group, C ₃ to C ₄₀ cycloalkyl group, Heterocycloalkyl group with 3 to 40 nuclear atoms, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphine group , is substituted or unsubstituted with one or more substituents selected from the group consisting of C ₆ ~ C ₆₀ mono or diarylphosphinyl group and C ₆ ~ C ₆₀ arylsilyl group, and when substituted with a plurality of substituents, they are the same as each other Or it may be different.

The present invention provides an organic electroluminescent device comprising 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 the compound of Formula 1. .

In the present invention, “alkyl” is a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms, examples of which include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, and hexyl. etc., but is not limited to this.

In the present invention, “alkenyl” is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond, examples of which include vinyl, Examples include allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

In the present invention, “alkynyl” is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond, examples of which include ethynyl. , 2-propynyl, etc., but is not limited thereto.

In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 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, but are not limited to, phenyl, naphthyl, phenanthryl, and anthryl.

In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 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 may be included, and it is further interpreted to include a condensed form with an aryl group. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; Polycyclics such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl ring; Examples include 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 means aryl having 5 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, where R' means 1 to 40 alkyl, and has a linear, branched or cyclic structure. It is interpreted as including. Examples of such 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 60 carbon atoms.

“Cycloalkyl” in the present invention 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, preferably 1 to 3 carbons in the ring, is N, O, It is substituted with a hetero atom such as S or 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 60 carbon atoms.

“Condensed ring” in the present invention means a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combination thereof.

Since the compound represented by Formula 1 according to the present invention has excellent thermal stability, hole transport, hole injection performance, electron transport and electron injection performance, and has excellent phosphorescence properties as a light emitting layer, it is preferably used as an organic material layer material of an organic electroluminescent device. Can be used as a light emitting layer material.

In particular, when the new compound represented by Formula 1 of the present invention is used as a light-emitting layer material, it is possible to manufacture an organic electroluminescent device with excellent light-emitting performance, low driving voltage, high efficiency, and long lifespan compared to conventional materials, and further improves performance and lifespan. This greatly improved full-color display panel can also be manufactured.

Hereinafter, the present invention will be described in detail.

1. Novel organic compounds

The new organic compound according to the present invention has a structure in which a fluorene group and a heterocycle are bonded to a carbazole moiety. By simultaneously containing carbazole and fluorene, which have hole transport properties, and a heterocyclic structure, which has a high electron transport structure, it has intramolecular polarity characteristics and can increase the binding force between holes and electrons in the light-emitting layer. Specifically, the new organic compound according to the present invention is characterized as a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, an arylene group of C ₆ to C ₁₈ and a heteroarylene group of 5 to 18 nuclear atoms;

Ar ₁ and Ar ₂ are each independently a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, and 3 to 40 nuclear atoms. Heterocycloalkyl group, C ₆ ~ 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 ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ is selected from the group consisting of a mono or diarylphosphinyl group and a C ₆ to C ₆₀ arylamine group;

a is an integer from 0 to 3;

b is an integer from 0 to 4;

R ₁ and R ₂ are each independently selected from deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₃ to 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 to C ₄₀ alkyloxy group, C ₆ to C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ is selected from the group consisting of an arylphosphine group, a C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and a C ₆ ~ C ₆₀ arylamine group, and when each of R ₁ and R ₂ is plural, they are the same or different from each other and;

R ₃ and R ₄ are each independently selected from the group consisting of a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;

The arylene group and heteroarylene group of L ₁ and L ₂ , the alkyl group, aryl group and heteroaryl group of Ar ₁ , Ar ₂ and R ₁ to R ₄ , and the Ar ₁ , Ar ₂ , R ₁ and R ₂ Alkenyl group, alkynyl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group, mono or diaryl phosphinyl group and aryl The silyl group is each independently deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₆ to C ₆₀ aryl group, Heteroaryl group with 5 to 60 nuclear atoms, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ arylamine group, C ₃ to C ₄₀ cycloalkyl group, Heterocycloalkyl group with 3 to 40 nuclear atoms, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphine group , is substituted or unsubstituted with one or more substituents selected from the group consisting of C ₆ ~ C ₆₀ mono or diarylphosphinyl group and C ₆ ~ C ₆₀ arylsilyl group, and when substituted with a plurality of substituents, they are the same as each other Or it may be different.

According to a preferred embodiment of the present invention, Ar ₁ may be selected from the group consisting of a phenyl group, a biphenyl group, a naphthalenyl group, a phenanthrenyl group, a triphenylenyl group, a fluorenyl group, and a carbazolyl group.

According to a preferred embodiment of the present invention, L ₁ and L ₂ may each independently be selected from the group consisting of a single bond, a phenylene group, a biphenylene group, a naphthalenyl group, a fluorenyl group, and a carbazolyl group.

According to a preferred embodiment of the present invention, L ₁ may be selected from the group consisting of a phenylene group, biphenylene group, naphthalenyl group, fluorenyl group, and carbazolyl group, and L ₂ may be a single bond or a phenylene group. there is.

According to a preferred embodiment of the present invention, Ar ₂ is preferably a substituent represented by any one of the following formulas 2 to 8 in order to extend life, improve luminous efficiency, and lower driving voltage, but is not limited thereto:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 2 to 8,

* refers to the part where the combination takes place;

Z ₁ to Z ₁₂ are each independently N or C(R ₅ );

In Formulas 3 and 8, any one of Z ₁ to Z ₄ bonded to L ₁ is C(R ₅ ), wherein R ₅ is absent;

Y ₁ is N(R ₆ ) or C(R ₇ )(R ₈ );

T ₁ is S, N(R ₆ ) or C(R ₇ )(R ₈ );

R ₅ to R ₈ are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₆ to C ₆₀ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₃ to C ₄₀ cycloalkyl group, 3 nuclear atoms to 40 heterocycloalkyl groups, C ₆ to C ₆₀ arylamine group, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to selected from the group consisting of a C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or diarylphosphinyl group, and a C ₆ to C ₆₀ arylsilyl group, or an adjacent group (e.g., L ₁ , another adjacent Ar ₁ , R ₅ , may be combined with R _6, R ₇ or R ₈ ) to form a condensed ring, and when there are more than one R ₅ , they may be the same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkylboron group, aryl group of R ₅ to R ₈ Boron group, arylphosphine group, mono or diarylphosphinyl group, and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ 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 alkylboron group, C ₆ ~ Substituted with one or more substituents selected from the group consisting of C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and C ₆ ~ C ₆₀ arylsilyl group. When substituted or unsubstituted and substituted with a plurality of substituents, they may be the same or different from each other.

According to a preferred embodiment of the present invention, Ar ₂ is a substituent represented by any of the following formulas A-1 to A-19, and when applied to an organic electroluminescent device, it extends the lifespan, improves luminous efficiency, and lowers the driving voltage. It is preferred, but not limited to:

In the above formulas A-1 to A-19,

* refers to the part where the combination takes place;

m and q are each independently integers from 0 to 4;

n is an integer from 0 to 3;

p is an integer from 0 to 2;

R ₉ and R ₁₀ are each independently deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C 40 alkenyl group, C ₂ to _{C 40 alkynyl} group, C ₆ to C ₆₀ Aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₃ to C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms Heterocycloalkyl group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ is selected from the group consisting of an arylphosphine group, a C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and a C ₆ ~ C ₆₀ arylsilyl group, or an adjacent group (for example, L ₁ , another adjacent R ₉ , or R ₁₀ ) may be combined to form a condensed ring, and when each of R ₉ and R ₁₀ is plural, they are the same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkylboron group, aryl group of R ₉ and R ₁₀ Boron group, arylphosphine group, mono or diarylphosphinyl group, and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ 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 alkylboron group, C ₆ ~ Substituted with one or more substituents selected from the group consisting of C ₆₀ arylboron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and C ₆ ~ C ₆₀ arylsilyl group. When substituted or unsubstituted and substituted with a plurality of substituents, they may be the same or different from each other.

According to a preferred embodiment of the present invention, R ₅ to R ₁₀ are each independently hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group with 5 to 60 nuclear atoms. may be selected from the military.

According to a preferred embodiment of the present invention, R ₅ to R ₁₀ are each independently selected from the group consisting of hydrogen, phenyl group, biphenyl group, naphthalenyl group, carbazolyl group, fluorenyl group, pyridinyl group, and pyrimidinyl group. can be selected

The compound represented by Formula 1 of the present invention may be represented by the following compounds, but is not limited thereto:

In the present invention, the compound represented by Formula 1 can be synthesized according to general synthetic methods (Chem. Rev., 60:313 (1960); J. Chem. SOC. 4482 (1955); Chem. Rev. 95: 2457 (1995), etc.). The detailed synthesis process for the compound of the present invention will be described in detail in the synthesis examples described later.

2. Organic electric field light emitting element

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

Specifically, the present invention is 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 is It includes a compound represented by Formula 1 above. At this time, the above compounds may be used alone or in combination of two or more.

The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light-emitting layer, a light-emitting auxiliary layer, a lifespan improvement layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, and at least one of these organic materials layers has the formula above. It may include a compound represented by 1. Preferably, the organic layer containing the compound represented by Formula 1 may be a light-emitting layer.

According to one example of the present invention, the light emitting layer of the organic electroluminescent device may include a host material, and in this case, the host material may include the compound represented by Formula 1 above. In this way, when the compound represented by Formula 1 is included as a light emitting layer material of an organic electroluminescent device, preferably a green phosphorescent host, the binding force between holes and electrons in the light emitting layer increases, thereby increasing the efficiency (light emission) of the organic electroluminescent device. efficiency and power efficiency), lifespan, brightness, and driving voltage can be improved.

The structure of the organic electroluminescent device according to the present invention described above is not particularly limited, and may be, for example, a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode are sequentially stacked. At this time, an electron transport auxiliary layer may be additionally laminated between the light emitting layer and the electron transport layer, and an electron injection layer may be additionally laminated on the electron transport layer. In the present invention, one or more of the hole injection layer, hole transport layer, light-emitting layer, electron transport layer, electron transport auxiliary layer, and electron injection layer may include a compound represented by Formula 1, and preferably the light-emitting layer is represented by Formula 1. It may contain the indicated compounds.

In addition, the structure of the organic electroluminescent device of the present invention may be one in which an anode, one or more organic material layers, and a cathode are sequentially stacked, and an insulating layer or adhesive layer is inserted at the interface between the electrode and the organic material layer.

The organic electroluminescent device of the present invention uses materials and methods known in the art, except that at least one of the organic layers (e.g., a light emitting layer) includes the compound represented by Formula 1 above. It can be manufactured by forming an organic material layer and an electrode.

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.

There is no particular limitation on the substrate that can be used in the present invention, and 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 SnO ₂ :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 LiO ₂ /Al, etc., but are not limited thereto.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited by the following examples.

[ Preparation example One] 2F3's synthesis

<Step 1> 3- chloro -9-phenyl- of carbazole synthesis

3-chloro-9H-carbazole (30 g, 148.8 mmol), iodobenzene (30.4 g, 148.8 mmol), Cu powder (4.7 g, 74.4 mmol), K ₂ CO ₃ (41.1 g, 297.5 mmol) under nitrogen stream. , nitrobenzene (600 ml) was mixed and stirred at 250°C for 12 hours.

After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer from which water was removed, and then purified by column chromatography to obtain 3-chloro-9-phenyl-carbazole (31 g, yield 75%).

¹ H-NMR: δ 7.08 (d, 1H), 7.18 (d, 1H), 7.56 (m, 7H), 7.87 (d, 1H), 8.04 (d, 1H), 8.21 (d, 1H)

<Step 2> 3- bromo -6- chloro -9-phenyl- of carbazole synthesis

Dissolve 3-chloro-9-phenyl-carbazole (30 g, 108.0 mmol) in acetonitrile and add NBS (19.2 g, 108.0 mmol) at 0°C. After adjusting the temperature to room temperature, stir for 12 hours. After completion by adding water, the organic layer was separated with methylene chloride and filtered using MgSO ₄ . After removing the solvent in the filtered organic layer, the target compound, 3-bromo-6-chloro-9-phenyl-carbazole (20 g, yield 52%), was obtained using column chromatography.

¹ H-NMR: δ 7.10 (d, 1H), 7.54 (m, 7H), 7.86 (d, 1H), 8.06 (d, 2H)

<Step 3> 3- chloro -6-(9,9-dimethyl-9H- fluorene -2-yl)-9-phenyl-9H- of carbazole synthesis

3-Bromo-6-chloro-9-phenyl-carbazole (20 g, 56.1 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (16 g, 67.3 mmol) under nitrogen stream. ), Pd(PPh ₃ ) ₄ (3.2 g, 5 mol%) and NaOH (6.7 g, 168.2 mmol) were added to 1000 ml/250 ml of THF/H ₂ O and stirred at 80°C for 12 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, 3-chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole (20.6), was purified using column chromatography. g, yield 78%) was obtained.

¹ H-NMR: δ 1.68(s, 6H) 7.08 (d, 1H), 7.26 (t, 1H), 7.36 (t, 1H), 7.57 (m, 6H), 7.79 (d, 2H), 7.87(d , 4H), 7.98(d, 1H), 8.08(d, 2H)

<Step 4> Synthesis of 2F3

3-Chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole (20 g, 42.6 mmol), 4,4,4',4 under nitrogen stream ',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (16.2 g, 63.8 mmol), Pd(dppf)Cl ₂ (17.4 g, 21.3 mmol), KOAc (8.4 g, 85.1 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130 for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 2F3 (17.2 g, yield 72%).

¹ H-NMR: δ 1.18 (s, 12H), 1.68 (s, 6H), 7.27 (t, 1H), 7.37 (t, 1H), 7.57 (m, 7H), 7.76 (d, 2H), 7.93 ( d, 6H), 8.07(d, 1H)

[ Preparation example 2] Synthesis of 1F3

<Step 1> 3- chloro -6-(9,9-dimethyl-9H- fluorene -1-yl)-9-phenyl-9H- of carbazole synthesis

3-Bromo-6-chloro-9-phenyl-carbazole (20 g, 56.1 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (16 g, 67.3 mmol) under nitrogen stream. ), Pd(PPh ₃ ) ₄ (3.2 g, 5 mol%) and NaOH (6.7 g, 168.2 mmol) were added to 1000 ml/500 ml of THF/H ₂ O and stirred at 80°C for 12 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, 3-chloro-6-(9,9-dimethyl-9H-fluoren-1-yl)-9-phenyl-9H-carbazole (20 g, yield 76%) was obtained.

¹ H-NMR: δ 1.68 (s, 6H), 7.06 (d, 1H), 7.26 (t, 1H), 7.35 (t, 1H), 7.63 (m, 8H), 7.79 (d, 1H), 7.89 ( d, 3H), 8.01(d, 2H), 8.06(d, 1H)

<Step 2> Synthesis of 1F3

3-Chloro-6-(9,9-dimethyl-9H-fluoren-1-yl)-9-phenyl-9H-carbazole (20 g, 42.6 mmol), 4,4,4',4 under nitrogen stream ',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (16.2 g, 63.8 mmol), Pd(dppf)Cl ₂ (17.4 g, 21.3 mmol), KOAc (8.4 g, 85.1 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130°C for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 1F3 (16.7 g, yield 70%).

¹ H-NMR: δ 1.18(s, 12H), 1.68(s, 6H), 7.26 (d, 1H), 7.35 (t, 1H), 7.57 (m, 9H), 7.75 (d, 1H), 7.95 ( d, 6H)

[Preparation Example 3] Synthesis of 2F2

<Step 1> 2- chloro -9-phenyl-9H- of carbazole synthesis

2-Chloro-9H-carbazole (30 g, 148.8 mmol), iodobenzene (30.4 g, 148.8 mmol), Cu powder (4.7 g, 74.4 mmol), K ₂ CO ₃ (41.1 g, 297.5 mmol) under nitrogen stream. , nitrobenzene (600 ml) was mixed and stirred at 250°C for 12 hours.

After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer from which water was removed, and then purified by column chromatography to obtain 2-chloro-9-phenyl-9H-carbazole (30.2 g, yield 73%).

¹ H-NMR: δ 6.99 (d, 1H), 7.21 (t, 1H), 7.57 (m, 8H), 8.18 (d, 1H), 8.36 (d, 1H)

<Step 2> 6- bromo -2- chloro -9-phenyl-9H- of carbazole synthesis

Dissolve 2-chloro-9-phenyl-9H-carbazole (30 g, 108.0 mmol) in acetonitrile, then dissolve NBS (19.2 g, 108.0 mmol) at 0°C, and then add NBS at 0°C. After adjusting the temperature to room temperature, stir for 12 hours. After completion by adding water, the organic layer was separated with methylene chloride and filtered using MgSO ₄ . After removing the solvent in the filtered organic layer, the target compound, 6-bromo-2-chloro-9-phenyl-9H-carbazole (16.6 g, yield 43%), was obtained using column chromatography.

¹ H-NMR: δ 7.02 (d, 1H), 7.48 (m, 8H), 8.04 (d, 1H), 8.36 (d, 1H)

<Step 3> 2- chloro -6-(9,9-dimethyl-9H- fluorene -2-yl)-9-phenyl-9H- of carbazole synthesis

6-Bromo-2-chloro-9-phenyl-9H-carbazole (15 g, 42.1 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (12 g, 50.5 mmol), Pd(PPh ₃ ) ₄ (2.4 g, 5 mol%) and NaOH (5.0 g, 126.2 mmol) were added to 400 ml/100 ml of THF/H ₂ O and stirred at 80°C for 12 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, 2-chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole (16.2), was purified using column chromatography. g, yield 82%) was obtained.

¹ H-NMR: δ 1.67 (s, 6H), 7.00 (d, 1H), 7.27 (t, 1H), 7.39 (m, 2H), 7.59 (m, 6H), 7.79 (d, 2H), 7.88 ( m, 3H), 7.98 (d, 1H), 8.08 (d, 1H), 8.36 (d, 1H)

<Step 4> Synthesis of 2F2

2-chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole (15 g, 31.9 mmol), 4,4,4',4 under nitrogen stream ',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (12.2 g, 47.9 mmol), Pd(dppf)Cl ₂ (13 g, 16 mmol), KOAc (6.3 g, 63.8 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130°C for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 2F2 (12 g, yield 67%).

¹ H-NMR: δ 1.18 (s, 12H), 1.68 (s, 6H), 7.25 (d, 1H), 7.40 (m, 2H), 7.54 (m, 6H), 7.79 (d, 3H), 7.88 ( m, 3H), 7.96 (d, 1H), 8.06 (d, 1H), 8.41 (d, 1H)

[Preparation Example 4] Synthesis of 3F2

<Step 1> 2- chloro -6-(9,9-dimethyl- fluorene -3-yl)-9-phenyl-9H- of carbazole synthesis

6-Bromo-2-chloro-9-phenyl-9H-carbazole (15 g, 42.1 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (12 g, 50.5 mmol), Pd(PPh ₃ ) ₄ (2.4 g, 5 mol%) and NaOH (5.0 g, 126.2 mmol) were added to 400 ml/100 ml of THF/H ₂ O and stirred at 80°C for 12 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, 2-chloro-6-(9,9-dimethyl-fluoren-3-yl)-9-phenyl-9H-carbazole (15.4 g, Yield 78%) was obtained.

¹ H-NMR: δ 1.68 (s, 6H), 7.03 (d, 1H), 7.31 (t, 1H), 7.42 (m, 2H), 7.65 (m, 9H), 7.91 (d, 2H), 8.01 ( d, 1H), 8.21 (s, 1H), 8.39 (d, 1H)

<Step 2> Synthesis of 3F2

2-Chloro-6-(9,9-dimethyl-fluoren-3-yl)-9-phenyl-9H-carbazole (15 g, 31.9 mmol), 4,4,4',4', under nitrogen stream. 5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (12.2 g, 47.9 mmol), Pd(dppf)Cl ₂ (13 g, 16 mmol), KOAc (6.3 g, 63.8 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130°C for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 3F2 (11.3 g, yield 63%).

¹ H-NMR: δ 1.18 (s, 12H), 1.68 (s, 6H), 7.29 (t, 1H), 7.43 (m, 2H), 7.72 (m, 10H), 7.91 (m, 2H), 8.02 ( d, 1H), 8.21 (s, 1H), 8.45 (d, 1H)

[Preparation Example 5] Synthesis of 2F1

<Step 1> Synthesis of 1-chloro-9-phenyl-carbazole

1-Chloro-9H-carbazole (30 g, 148.8 mmol), iodobenzene (30.4 g, 148.8 mmol), Cu powder (4.7 g, 74.4 mmol), K ₂ CO ₃ (41.1 g, 297.5 mmol) under nitrogen stream. , nitrobenzene (600 ml) was mixed and stirred at 250°C for 12 hours.

After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer from which water was removed, and then purified by column chromatography to obtain 1-chloro-9-phenyl-carbazole (29.8 g, yield 72%).

¹ H-NMR: δ 7.11 (d, 1H), 7.22 (t, 2H), 7.59 (m, 7H), 8.22 (d, 1H), 8.45 (d, 1H)

<Step 2> 6- bromo -One- chloro -9-phenyl- of carbazole synthesis

Dissolve 1-chloro-9-phenyl-carbazole (30 g, 108.0 mmol) in acetonitrile and add NBS (19.2 g, 108.0 mmol) at 0°C. After adjusting the temperature to room temperature, stir for 12 hours. After completion by adding water, the organic layer was separated with methylene chloride and filtered using MgSO ₄ . After removing the solvent in the filtered organic layer, the target compound, 6-bromo-1-chloro-9-phenyl-carbazole (15 g, yield 39%), was obtained using column chromatography.

¹ H-NMR: δ 7.11 (d, 1H), 7.21 (t, 1H), 7.52 (m, 7H), 8.07 (s, 1H), 8.45 (d, 1H)

<Step 3> Synthesis of 1-chloro-6-(9,9-dimethyl-fluoren-2-yl)-9-phenyl-carbazole

6-Bromo-1-chloro-9-phenyl-carbazole (15 g, 42.1 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (12 g, 50.5 mmol) under nitrogen stream. ), Pd(PPh ₃ ) ₄ (2.4 g, 5 mol%) and NaOH (5.0 g, 126.2 mmol) were added to 400 ml/100 ml of THF/H ₂ O and stirred at 80°C for 12 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, 1-chloro-6-(9,9-dimethyl-fluoren-2-yl)-9-phenyl-carbazole (16.2 g, yield 82) was obtained using column chromatography. %) was obtained.

¹ H-NMR: δ 1.68 (s, 6H), 7.12 (d, 1H), 7.25 (t, 2H), 7.41 (t, 1H), 7.57 (m, 6H), 7.80 (d, 2H), 7.92 ( m, 3H), 8.02 (d, 1H), 8.11 (d, 1H), 8.46 (d, 1H)

<Step 4> Synthesis of 2F1

1-Chloro-6-(9,9-dimethyl-fluoren-2-yl)-9-phenyl-carbazole (15 g, 31.9 mmol), 4,4,4',4',5, under nitrogen stream. 5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (12.2 g, 47.9 mmol), Pd(dppf)Cl ₂ (13 g, 16 mmol) ), KOAc (6.3 g, 63.8 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130°C for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 2F1 (11.8 g, yield 66%).

¹ H-NMR: δ 1.18 (s, 12H), 1.68 (s, 6H), 7.27 (t, 2H), 7.42 (t, 1H), 7.55 (m, 7H), 7.76 (d, 2H), 7.91 ( m, 3H), 8.00 (d, 1H), 8.10 (d, 1H), 8.57 (d, 1H)

[Preparation Example 6] Synthesis of 4F1

<Step 3> 1- chloro -6-(9,9-dimethyl- fluorene -4-yl)-9-phenyl- of carbazole synthesis

6-Bromo-1-chloro-9-phenyl-carbazole (15 g, 42.1 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (12 g, 50.5 mmol) under nitrogen stream. ), Pd(PPh ₃ ) ₄ (2.4 g, 5 mol%) and NaOH (5.0 g, 126.2 mmol) were added to 400 ml/100 ml of THF/H ₂ O and stirred at 80°C for 12 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, 1-chloro-6-(9,9-dimethyl-fluoren-4-yl)-9-phenyl-carbazole (15.8 g, yield 80 %) was obtained.

¹ H-NMR: δ 1.68 (s, 6H), 7.11 (d, 1H), 7.25 (t, 2H), 7.52 (m, 9H), 7.79 (d, 2H), 7.92 (m, 2H), 7.98 ( d, 1H), 8.45 (d, 1H)

<Step 4> Synthesis of 4F1

1-Chloro-6-(9,9-dimethyl-fluoren-4-yl)-9-phenyl-carbazole (15 g, 31.9 mmol), 4,4,4',4',5, under nitrogen stream. 5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (12.2 g, 47.9 mmol), Pd(dppf)Cl ₂ (13 g, 16 mmol) ), KOAc (6.3 g, 63.8 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130°C for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 4F1 (11.3 g, yield 63%).

¹ H-NMR: δ 1.18 (s, 12H), 1.68 (s, 6H), 7.27 (t, 2H), 7.41 (t, 1H), 7.57 (m, 9H), 7.80 (d, 2H), 7.91 ( m, 2H), 7.98 (d, 1H), 8.57 (d, 1H)

[ Preparation example 7] 2F4's synthesis

<Step 1> 4- chloro -9-phenyl-9H- of carbazole synthesis

4-chloro-9H-carbazole (30 g, 148.8 mmol), iodobenzene (30.4 g, 148.8 mmol), Cu powder (4.7 g, 74.4 mmol), K ₂ CO ₃ (41.1 g, 297.5 mmol) under nitrogen stream. , nitrobenzene (600 ml) was mixed and stirred at 250°C for 12 hours.

After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer from which water was removed, and then purified by column chromatography to obtain 4-chloro-9-phenyl-9H-carbazole (31 g, yield 75%).

¹ H-NMR: δ 6.97 (d, 1H), 7.23 (t, 2H), 7.57 (m, 7H), 7.84 (d, 1H), 8.21 (d, 1H)

<Step 2> 6- bromo -4- chloro -9-phenyl-9H- of carbazole synthesis

Dissolve 4-chloro-9-phenyl-9H-carbazole (30 g, 108.0 mmol) in acetonitrile and add NBS (19.2 g, 108.0 mmol) at 0°C. After adjusting the temperature to room temperature, stir for 12 hours. After completion by adding water, the organic layer was separated with methylene chloride and filtered using MgSO ₄ . After removing the solvent in the filtered organic layer, the target compound, 6-bromo-4-chloro-9-phenyl-9H-carbazole (12.7 g, yield 33%), was obtained using column chromatography.

¹ H-NMR: δ 7.03 (d, 1H), 7.29 (t, 1H), 7.53 (m, 7H), 7.81 (d, 1H), 8.07 (s, 1H)

<Step 3> 4- chloro -6-(9,9-dimethyl-9H- fluorene -2-yl)-9-phenyl-9H- of carbazole synthesis

6-Bromo-4-chloro-9-phenyl-9H-carbazole (12 g, 33.6 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (9.6 g, 40.4 mmol), Pd(PPh ₃ ) ₄ (1.9 g, 5 mol%) and NaOH (4.0 g, 100.9 mmol) were added to 400 ml/100 ml of THF/H ₂ O and stirred at 80°C for 12 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, 4-chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole (12.2 g, yield 77%) was obtained.

¹ H-NMR: δ 1.68 (s, 6H), 7.02 (d, 1H), 7.29 (t, 2H), 7.40 (t, 1H), 7.61 (m, 6H), 7.81 (d, 3H), 7.92 ( m, 3H), 8.01 (d, 1H), 8.11 (d, 1H)

<Step 4> Synthesis of 2F4

4-Chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole (12 g, 25.5 mmol), 4,4,4',4 under nitrogen stream. ',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (9.7 g, 38.3 mmol), Pd(dppf)Cl ₂ (10.4 g, 12.8 mmol), KOAc (5 g, 63 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130°C for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 2F4 (8.9 g, yield 62%).

¹ H-NMR: δ 1.18 (s, 12H), 1.68 (s, 6H), 7.35 (m, 4H), 7.59 (m, 6H), 7.81 (d, 2H), 7.92 (m, 5H), 8.08 ( d, 1H)

[ Preparation example 8] 3F4's synthesis

<Step 1> 4- chloro -6-(9,9-dimethyl-9H- fluorene -3-yl)-9-phenyl-9H- of carbazole synthesis

6-Bromo-4-chloro-9-phenyl-9H-carbazole (12 g, 33.6 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (9.6 g, 40.4 mmol), Pd(PPh ₃ ) ₄ (1.9 g, 5 mol%) and NaOH (4.0 g, 100.9 mmol) were added to 400 ml/100 ml of THF/H ₂ O and stirred at 80°C for 12 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, 4-chloro-6-(9,9-dimethyl-9H-fluoren-3-yl)-9-phenyl-9H-carbazole (12.5 g, yield 79%) was obtained.

¹ H-NMR: δ 1.68 (s, 6H), 7.02 (d, 1H), 7.31 (t, 2H), 7.36 (t, 1H), 7.77 (m, 10H), 7.92 (m, 2H), 8.01 ( d, 1H), 8.22 (s, 1H)

<Step 2> Synthesis of 3F4

4-chloro-6-(9,9-dimethyl-9H-fluoren-3-yl)-9-phenyl-9H-carbazole (12 g, 25.5 mmol), 4,4,4',4 under nitrogen stream ',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxabororane) (9.7 g, 38.3 mmol), Pd(dppf)Cl ₂ (10.4 g, 12.8 mmol), KOAc (5 g, 63 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130°C for 12 hours.

After the reaction was completed, extraction was performed with ethyl acetate, moisture was removed with MgSO ₄ , and purification was performed by column chromatography to obtain 3F4 (8.6 g, yield 60%).

¹ H-NMR: δ 1.18 (s, 12H), 1.68 (s, 6H), 7.37 (m, 4H), 7.65 (m, 9H), 7.95 (m, 4H), 7.20 (s, 1H)

[Synthesis Example 1] Synthesis of C-1

2F3 (10 g, 17.8 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.8 g, 17.8 mmol), Pd(PPh ₃ ) ₄ under nitrogen stream. (1.0 g, 5 mol%) and NaOH (2.1 g, 53.4 mmol) were added to 100 ml/50 ml of THF/H ₂ O and stirred at 80°C for 12 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 C-1 (10.1 g, yield 85%) was obtained using column chromatography.

Mass : [(M+H) ⁺ ] : 667

[Synthesis Example 2] Synthesis of C-5

2F3 (10 g, 17.8 mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (6.1 g, 17.8 mmol), Pd(PPh ₃ ) ₄ (1.0 g, 5 mol%) and NaOH (2.1 g, 53.4 mmol) were added to 100 ml/50 ml of THF/H ₂ O and stirred at 80°C for 12 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, C-5 (11 g, yield 83%), was obtained using column chromatography.

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 3] Synthesis of C-11

2F3 (10 g, 17.8 mmol), 2-(3-bromophenyl)-4,6-diphenylpyrimidine (6.9 g, 17.8 mmol), Pd(PPh ₃ ) ₄ under nitrogen stream. (1.0 g, 5 mol%) and NaOH (2.1 g, 53.4 mmol) were added to 100 ml/50 ml of THF/H ₂ O and stirred at 80°C for 12 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, C-11 (11.4 g, yield 86%), was obtained using column chromatography.

Mass : [(M+H) ⁺ ] : 742

[Synthesis Example 4] Synthesis of C-35

1F3 (10 g, 17.8 mmol), 2-chloro-4,6-di(naphthalen-2-yl)-1,3,5-triazine (6.6 g, 17.8 mmol), Pd(PPh ₃ ) under nitrogen stream. ₄ (1.0 g, 5 mol%) and NaOH (2.1 g, 53.4 mmol) were added to 100 ml/50 ml of THF/H ₂ O and stirred at 80°C for 12 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, C-35 (11.5 g, yield 84%), was obtained using column chromatography.

Mass : [(M+H) ⁺ ] : 767

[Synthesis Example 5] Synthesis of C-37

1F3 (10 g, 17.8 mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (6.9 g, 17.8 mmol), Pd(PPh ₃ ) under nitrogen stream. ₄ (1.0 g, 5 mol%) and NaOH (2.1 g, 53.4 mmol) were added to 100 ml/50 ml of THF/H ₂ O and stirred at 80°C for 12 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, C-37 (11.5 g, yield 87%) was obtained using column chromatography.

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 6] Synthesis of C-38

1F3 (10 g, 17.8 mmol), 4-(4-bromophenyl)-3,5-diphenyl-1,2,4-triazole (6.7 g, 17.8 mmol), Pd(PPh ₃ ) under nitrogen stream. ₄ (1.0 g, 5 mol%) and NaOH (2.1 g, 53.4 mmol) were added to 100 ml/50 ml of THF/H ₂ O and stirred at 80°C for 12 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, C-38 (10.9 g, yield 84%) was obtained using column chromatography.

Mass : [(M+H) ⁺ ] : 731

[Synthesis Example 7] Synthesis of C-113

The target compound, C-113 (9.5 g, yield 81%), was obtained by performing the same procedure as in Synthesis Example 1 except that 2F2 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 667

[Synthesis Example 8] Synthesis of C-117

The target compound C-117 (10.3 g, yield 78%) was obtained by performing the same process as Synthesis Example 2 except that 2F2 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 9] Synthesis of C-123

The target compound C-123 (10.8 g, yield 82%) was obtained by performing the same process as Synthesis Example 3 except that 2F2 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 742

[Synthesis Example 10] Synthesis of C-175

The target compound C-175 (11.3 g, yield 83%) was obtained by performing the same process as Synthesis Example 4 except that 3F3 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 767

[Synthesis Example 11] Synthesis of C-177

The target compound C-177 (10.2 g, yield 77%) was obtained by performing the same process as Synthesis Example 5 except that 3F2 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 12] Synthesis of C-178

The target compound C-178 (10.4 g, yield 80%) was obtained by performing the same process as Synthesis Example 6 except that 3F2 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 731

[Synthesis Example 13] Synthesis of C-225

The target compound C-113 (8.9 g, yield 76%) was obtained by performing the same procedure as in Synthesis Example 1 except that 2F1 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 667

¹ H-NMR: δ 1.68 (s, 6H), 7.27 (t, 1H), 7.48 (m, 14H), 7.79 (d, 2H), 7.92 (m, 3H), 7.98 (d, 1H), 8.07 ( d, 1H), 8.40 (d, 5H)

[Synthesis Example 14] Synthesis of C-229

The target compound, C-229 (9.9 g, yield 75%), was obtained by performing the same procedure as in Synthesis Example 2, except that 2F1 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 15] Synthesis of C-235

The target compound C-123 (10.3 g, yield 78%) was obtained by performing the same procedure as in Synthesis Example 3 except that 2F1 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 742

[Synthesis Example 16] Synthesis of C-315

The target compound, C-315 (11.2 g, yield 82%), was obtained by performing the same procedure as in Synthesis Example 4 except that 4F1 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 767

[Synthesis Example 17] Synthesis of C-317

The target compound, C-317 (10.5 g, yield 79%), was obtained by performing the same procedure as in Synthesis Example 5 except that 4F1 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 18] Synthesis of C-318

The target compound C-178 (10.5 g, yield 81%) was obtained by performing the same procedure as in Synthesis Example 6 except that 4F1 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 731

[Synthesis Example 19] Synthesis of C-337

The target compound, C-337 (9.4 g, yield 80%), was obtained by performing the same procedure as in Synthesis Example 1 except that 2F4 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 667

[Synthesis Example 20] Synthesis of C-341

The target compound C-341 (10.8 g, yield 82%) was obtained by performing the same procedure as in Synthesis Example 2 except that 2F4 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 21] Synthesis of C-347

The target compound, C-347 (10.4 g, yield 79%), was obtained by performing the same procedure as in Synthesis Example 3, except that 2F4 (10 g, 17.8 mmol) was used instead of 2F3.

Mass : [(M+H) ⁺ ] : 742

[Synthesis Example 22] Synthesis of C-399

The target compound, C-399 (10.5 g, yield 77%), was obtained by performing the same procedure as in Synthesis Example 4 except that 3F4 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 767

[Synthesis Example 23] Synthesis of C-401

The same process as Synthesis Example 5 was performed except that 3F4 (10 g, 17.8 mmol) was used instead of 1F3 to obtain the target compound, C-401 (11 g, yield 83%).

Mass : [(M+H) ⁺ ] : 743

[Synthesis Example 24] Synthesis of C-402

The target compound, C-402 (9.6 g, yield 74%), was obtained by performing the same procedure as in Synthesis Example 6 except that 3F4 (10 g, 17.8 mmol) was used instead of 1F3.

Mass : [(M+H) ⁺ ] : 731

[ Example 1 to 24] Green Organic electric field Fabrication of light emitting devices

Compounds C-1 to C-402 synthesized in Synthesis Examples 1 to 24 were purified to high purity by sublimation using a commonly known method, and then a green organic electroluminescent device was manufactured according to the process below.

First, a glass substrate coated with a 1500 Å thin film of ITO (indium tin oxide) 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)/each compound of C-1 to C-402 + 10% Ir(ppy) ₃ (30nm)/BCP (10 nm)/Alq An organic electroluminescent device was manufactured by stacking ₃ (30 nm)/LiF (1 nm)/Al (200 nm) in the order.

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

[ Comparative example 1] Green Organic electric field Fabrication of light emitting devices

A green organic electroluminescent device was manufactured in the same process as Example 1, except that CBP was used instead of Compound C-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 (10) mA/cm2 were measured for each green organic electroluminescent device manufactured in Examples 1 to 24 and Comparative Example 1, and the results are shown in Table 1 below. indicated.

Sample host driving voltage
(V) EL peak
(nm) Current efficiency
(cd/A) Example 1 C-1 6.32 516 40.2 Example 2 C-5 6.21 517 42.3 Example 3 C-11 6.24 516 44.8 Example 4 C-35 6.35 518 40.5 Example 5 C-37 6.48 516 46.2 Example 6 C-38 6.42 516 42.6 Example 7 C-113 6.73 516 43.6 Example 8 C-117 6.42 517 41.7 Example 9 C-123 6.48 518 46.3 Example 10 C-175 6.29 516 43.2 Example 11 C-177 6.19 517 47.6 Example 12 C-178 6.34 516 42.8 Example 13 C-225 6.23 518 46.2 Example 14 C-229 6.38 517 45.4 Example 15 C-235 6.49 516 47.3 Example 16 C-315 6.33 518 45.1 Example 17 C-317 6.18 516 43.5 Example 18 C-318 6.48 516 46.5 Example 19 C-337 6.28 517 44.2 Example 20 C-341 6.48 518 42.8 Example 21 C-347 6.73 516 47.4 Example 22 C-399 6.63 518 43.2 Example 23 C-401 6.47 516 46.8 Example 24 C-402 6.28 517 42.6 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, when the compounds (C-1 to C-402) according to the present invention were used as the emission layer of a green organic electroluminescent device (Examples 1 to 24), green organic electroluminescence using conventional CBP Compared to the device (Comparative Example 1), it can be seen that it exhibits better performance in terms of efficiency and driving voltage.

Claims (9)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
L ₁ and L ₂ are each independently a single bond or a C ₆ to C ₁₈ arylene group;
Ar ₁ is an aryl group of C ₆ to C ₆₀ ;
Ar ₂ is a substituent represented by any one of the following formulas A-8 to A-19;

In the above formulas A-8 to A-19,
* refers to the part where the combination takes place;
m and q are each independently integers from 0 to 4;
n is an integer from 0 to 3;
p is an integer from 0 to 2;
R ₉ and R ₁₀ are each independently deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C 40 alkenyl group, C ₂ to _{C 40 alkynyl} group, C ₆ to C ₆₀ Aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₃ to C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms Heterocycloalkyl group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ may be selected from the group consisting of an arylphosphine group, a C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and a C ₆ ~ C ₆₀ arylsilyl group, or may be combined with an adjacent group to form a condensed ring, and the R When each of ₉ and R ₁₀ is plural, they are the same or different from each other;
a is 0;
b is 0;
R ₁ and R ₂ are each independently selected from deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₃ to 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 to C ₄₀ alkyloxy group, C ₆ to C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ is selected from the group consisting of an arylphosphine group, a C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and a C ₆ ~ C ₆₀ arylamine group, and when each of R ₁ and R ₂ is plural, they are the same or different from each other and;
R ₃ and R ₄ are each independently an alkyl group of C ₁ to C ₄₀ ;
The arylene group of L ₁ and L ₂ , the aryl group of Ar ₁ , the alkyl group of R ₃ and R ₄ , the alkyl group of R ₁ and R ₂ , 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, mono or Diarylphosphinyl group and arylsilyl group and the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group of R ₉ and R ₁₀ , Alkylsilyl group, alkylboron group, arylboron group, arylphosphine group, mono or diarylphosphinyl group, and arylsilyl group each independently carry deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ ~C ₄₀ alkenyl group, C ₂ ~C ₄₀ alkynyl group, C ₆ ~C ₆₀ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C ₆ ~C ₆₀ aryloxy group, C ₁ ~C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ 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 ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphine group, C ₆ ~ C ₆₀ mono or diarylphosphinyl group, and C ₆ ~ C ₆₀ arylsilyl group. When substituted or unsubstituted with one or more substituents selected from the group and substituted with a plurality of substituents, these may be the same or different from each other. delete delete delete According to paragraph 1,
Ar ₁ is a compound selected from the group consisting of a phenyl group, biphenyl group, naphthalenyl group, phenanthrenyl group, triphenylenyl group, and fluorenyl group. According to paragraph 1,
Wherein L ₁ and L ₂ are each independently a compound selected from the group consisting of a single bond, a phenylene group, a biphenylene group, a naphthalenyl group, and a fluorenyl group. According to paragraph 1,
The compound represented by Formula 1 is characterized in that it is selected from the group consisting of the following compounds:















An organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic material layers interposed between the anode and the cathode,
An organic electroluminescent device, wherein at least one of the one or more organic layers includes the compound represented by the formula (1) of claim 1. According to clause 8,
The organic material layer containing the compound is an organic electroluminescent device selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron transport auxiliary layer, an electron injection layer, a lifespan improvement layer, a light emitting layer, and a light emitting auxiliary layer.