KR102591468B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same}

The present invention relates to novel compounds and organic light-emitting devices containing them.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

The development of new materials for organic materials used in organic light-emitting devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to novel compounds and organic light-emitting devices containing them.

The present invention relates to a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

Each X is independently N or CH, but two or more of the Xs are N,

Y is O or S,

L ₁ is a direct bond, or substituted or unsubstituted C _6-60 arylene,

L ₂ is a direct bond, or a substituted or unsubstituted C _6-60 arylene,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _6- containing one or more heteroatoms selected from the group consisting of O and S. ₆₀ heteroaryl,

R ₁ is substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _6-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S,

R ₂ is each independently hydrogen or deuterium,

However, at least one of Ar ₁ , Ar ₂ and R ₁ is substituted with one or more deuterium, or at least one of R ₂ is deuterium.

The compound represented by the above-described formula 1 can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device.

In particular, the compound represented by the above-mentioned formula 1 can be used as a hole injection, hole transport, hole injection and transport, light emitting, electron transport, or electron injection material.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron injection and transport layer 5, and a cathode 6.
Figure 2 shows a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and a cathode 6. An example of an organic light-emitting device is shown.

Hereinafter, the present invention will be described in more detail to aid understanding.

(Definition of Terms)

는 다른 치환기에 연결되는 결합을 의미한다.In this specification, and

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" refers to deuterium, halogen group, cyano group, nitro group, hydroxy group, carbonyl group, ester group, imide group, amino group, phosphine oxide group, alkoxy group, aryloxy group, alkyl group. Thioxy group, arylthioxy group, alkylsulfoxy group, arylsulfoxy group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamine group, aralkylamine substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroarylamine group, an arylamine group, an arylphosphine group, or a heteroaryl containing one or more of N, O, and S atoms; It means that two or more of the substituents exemplified above are substituted or unsubstituted. For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

In the present specification, the silyl group specifically includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited to this.

In the present specification, the boron group specifically includes trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, and phenyl boron group, but is not limited thereto.

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n. -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group, etc., but are not limited to these.

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

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group with aromaticity. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, perylenyl group, chrysenyl group, etc., but is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as a heteroelement, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, phenothiazinyl group, and dibenzofuranyl group, but are not limited to these.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example of the aryl group described above. In this specification, the aralkyl group, alkylaryl group, and alkylamine group are the same as the examples of the alkyl group described above. In the present specification, the description regarding heteroaryl described above may be applied to heteroaryl among heteroarylamines. In this specification, the alkenyl group among the aralkenyl groups is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above can be applied, except that arylene is a divalent group. In the present specification, the description of heteroaryl described above can be applied, except that heteroarylene is a divalent group. In the present specification, the description of the aryl group or cycloalkyl group described above can be applied, except that the hydrocarbon ring is not monovalent and is formed by combining two substituents. In the present specification, the description of heteroaryl described above can be applied, except that the heterocycle is not monovalent and is formed by combining two substituents.

(compound)

The present invention provides a compound represented by Formula 1 above.

Hereinafter, Formula 1 and the compounds represented by this formula will be described in detail as follows.

X is each independently N or CH; Two or more of the above X are N.

Specifically, all X may be N.

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _6- containing one or more heteroatoms selected from the group consisting of O and S. ₆₀ may be heteroaryl.

Specifically, Ar ₁ and Ar ₂ are each independently selected from phenyl, biphenylyl, naphthyl, naphthyl phenyl, phenanthrenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, dibenzofuranyl. , or it may be dibenzothiophenyl. In this case, Ar ₁ and Ar ₂ are unsubstituted; It may be substituted with one or more deuterium.

For example, Ar ₁ and Ar ₂ are each independently unsubstituted biphenylyl, naphthyl, phenanthrenyl, naphthylphenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, 9-phenyl. -9H-carbazolyl, or phenyl unsubstituted or substituted with 5 deuterium atoms.

L ₁ may be a direct bond, or substituted or unsubstituted C _6-60 arylene.

For example, L ₁ may be a direct bond, phenylene, biphenylene, or naphthylene.

L ₂ may be a direct bond, or substituted or unsubstituted C _6-60 arylene.

For example, L ₁ may be a direct bond or phenylene.

Y may be O or S, such as O.

R ₁ may be substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _6-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O, and S.

For example, R ₁ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl; R ₁ may be unsubstituted or substituted with one or more deuterium.

R ₂ may each independently be hydrogen or deuterium.

However, Formula 1 satisfies the above definition and at the same time, at least one of Ar ₁ , Ar ₂ and R ₁ is substituted with one or more deuterium, or at least one of R ₂ is deuterium.

For a more specific example, the compound represented by Formula 1 may be any one selected from the group consisting of the following compounds:

Additionally, the present invention provides a method for producing a compound represented by Chemical Formula 1, as shown in Scheme 1 below.

[Scheme 1]

In _{Scheme 1 , the definitions of} Also, in Scheme 1, Z is halogen, preferably chloro.

Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed according to what is known in the art. The manufacturing method may be further detailed in the manufacturing examples described later.

(Organic light emitting device)

Meanwhile, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. For example, the present invention is an organic light emitting device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, An organic light-emitting device is provided wherein at least one of the organic material layers contains a compound represented by Formula 1 above.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited to this and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, the hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 Contains the indicated compounds.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer includes the compound represented by Formula 1.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light-emitting device of the present invention is an organic material layer that, in addition to the light-emitting layer, further includes a hole injection layer and a hole transport layer between the first electrode and the light-emitting layer, and an electron transport layer and an electron injection layer between the light-emitting layer and the second electrode. It can have a structure that does. However, the structure of the organic light emitting device is not limited to this and may include fewer or more organic layers.

In addition, the organic light emitting device according to the present invention is a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate where the first electrode is an anode and the second electrode is a cathode. It may be a device. In addition, the organic light emitting device according to the present invention is an inverted type organic device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate where the first electrode is a cathode and the second electrode is an anode. It may be a light emitting device. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron injection and transport layer 5, and a cathode 6. In this structure, the compound represented by Formula 1 may be included in the hole transport layer.

Figure 2 shows a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and a cathode 6. An example of an organic light-emitting device is shown. In this structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the electron suppression layer.

The organic light emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Additionally, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

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

Additionally, the compound represented by Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

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

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), metal oxides such as indium zinc oxide (IZO), ZnO: Combinations of metals and oxides such as Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole and polyaniline. There are similar conductive polymers, but they are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof, LiF/Al or LiO ₂ /Al. There are multi-layered structures, but they are not limited to these.

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. These include organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. The hole transport material is a material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and has high mobility for holes. The material is suitable. As the hole transport material, a compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having both a conjugated and non-conjugated portion may be used, but is not limited thereto. .

The electron blocking layer is formed on the hole transport layer, preferably in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. This refers to the layer that plays a role in improving. The electron blocking layer includes an electron blocking material, and examples of the electron blocking material include the compound represented by Chemical Formula 1, or an arylamine-based organic material, but are not limited thereto.

The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole, and benz. Examples include, but are not limited to, imidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene.

The light emitting layer may include a host material and a dopant material as described above. The host material may further include a condensed aromatic ring derivative or a heterocyclic ring-containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene, and styrylamine compounds include substituted or unsubstituted arylamino groups. It is a compound in which at least one arylvinyl group is substituted on the arylamine, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The hole blocking layer is formed on the light-emitting layer, preferably in contact with the light-emitting layer, to improve the efficiency of the organic light-emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling. It refers to the layer that plays a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include azine derivatives including triazine, triazole derivatives, oxadiazole derivatives, phenanthroline derivatives, and phosphine oxide derivatives, which are introduced with electron-withdrawing groups. Any compound may be used, but is not limited thereto.

The electron injection and transport layer is a layer that simultaneously performs the roles of an electron transport layer and an electron injection layer, injecting electrons from an electrode and transporting the received electrons to the light-emitting layer, and is formed on the light-emitting layer or the hole blocking layer. As such an electron injection and transport material, a material that can easily inject electrons from the cathode and transfer them to the light emitting layer, and a material with high mobility for electrons, is suitable. Specific examples of electron injection and transport materials include, but are not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq ₃ , organic radical compounds, hydroxyflavone-metal complexes, and triazine derivatives. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds. , or a nitrogen-containing 5-membered ring derivative, etc., but is not limited thereto.

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, Tris(2-methyl-8-hydroxyquinolinato)aluminum, Tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

The organic light-emitting device according to the present invention may be a bottom-emitting device, a top-emitting device, or a double-sided light-emitting device. In particular, it may be a bottom-emitting device that requires relatively high luminous efficiency.

Additionally, the compound represented by Formula 1 may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.

[Manufacturing example]

Preparation Example 1: Preparation of compound sub 1-2

First, compound A-1 was prepared.

2-Bromo-6-fluorophenol (100 g, 526.5 mmol) and (4-chloro-2-fluorophenyl)boronic acid (91.6 g, 526.5 mmol) were added to tetrahydrofuran (2000 ml) in a nitrogen atmosphere. It was added, stirred and refluxed. Afterwards, potassium carbonate (218.3 g, 1579.4 mmol) was dissolved in water (218 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (18.2 g, 15.8 mmol) was added. After reaction for 1 hour, it was cooled to room temperature and the resulting solid was filtered. The solid was dissolved in chloroform (6739 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare gray solid Compound A-1 (99.7 g, yield 74%, MS: [M+H] ⁺ = 257).

Next, compound A-2 was prepared.

In a nitrogen atmosphere, A-1 (70 g, 273.4 mmol) and N-bromo succinamide (48.7 g, 273.4 mmol) were added to chloroform (350 ml), stirred, and cooled to 0°C. After reacting for 1 hour, it was cooled to room temperature and water was added. Afterwards, the organic layer and the water layer were separated, and the organic layer was concentrated. This was again dissolved in chloroform (913 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare white solid Compound A-2 (65.7 g, yield 72%, MS: [M+H] ⁺ = 334.9).

Next, compound A-3 was prepared.

In a nitrogen atmosphere, A-2 (50 g, 149.7 mmol) was added to dimethylformamide (250 ml), potassium carbonate was added, and the mixture was stirred and heated to 140°C. After reacting for 7 hours, it was cooled to room temperature and water was added. Afterwards, the formed solid was filtered. This was dissolved in chloroform (380 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare white solid Compound A-2 (27 g, yield 71%, MS: [M+H] ⁺ = 255).

Next, compound A-4 was prepared.

In a nitrogen atmosphere, A-3 (20 g, 67.1 mmol) and phenyl boronic acid (8.2 g, 67.1 mmol) were added to tetrahydrofuran (400 ml), stirred, and refluxed. Afterwards, potassium carbonate (27.8 g, 201.4 mmol) was dissolved in water (28 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (397 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare white solid compound A-4 (14.9 g, yield 75%, MS: [M+H] ⁺ = 297).

Afterwards, compound sub 1-1 was prepared.

A-4 (15 g, 50.7 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (8.8 g, 50.7 mmol) were added to dimethylformamide (300 ml) and stirred in a nitrogen atmosphere. and refluxed. Afterwards, potassium triphosphate (32.3 g, 152 mmol) was added, stirred sufficiently, reacted for 3 hours, cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (228 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare white solid compound sub 1-1 (16.8 g, yield 74%, MS: [M+H] ⁺ = 450.2).

Afterwards, compound sub 1-2 was prepared.

In a nitrogen atmosphere, sub 1-1 (15 g, 33.4 mmol) and bis(pinacolato)diboron (9.3 g, 36.7 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium acetate (9.6 g, 100.2 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1 mmol) and tricyclohexylphosphine (0.6 g, 2 mmol) were added. did. After reacting for 7 hours, the reaction mixture was cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (181 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethanol to prepare white solid compound sub 1-2 (15.9 g, yield 88%, MS: [M+H] ⁺ = 542.3).

Preparation Example 2: Preparation of compound sub 2-2

First, compound sub 2-1 was prepared.

A-4 (15 g, 50.7 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-D8 (8.9 g, 50.7 mmol) were mixed with dimethylformamide (300 ml) in a nitrogen atmosphere. ) and stirred and refluxed. Afterwards, potassium triphosphate (32.3 g, 152 mmol) was added, stirred sufficiently, and reacted for 7 hours. After cooling to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (229 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare white solid compound sub 1-2 (13.7 g, yield 60%, MS: [M+H] ⁺ = 452.2).

Next, compound sub 2-2 was prepared.

In a nitrogen atmosphere, sub 2-1 (15 g, 33.2 mmol) and bis(pinacolato)diboron (9.3 g, 36.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium acetate (9.6 g, 99.7 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1 mmol) and tricyclohexylphosphine (0.6 g, 2 mmol) were added. did. After reacting for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (181 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethanol to prepare white solid compound sub 2-2 (10.3 g, yield 57%, MS: [M+H] ⁺ = 544.3).

Preparation Example 3: Preparation of compound sub 3-2

First, compound B-1 was prepared.

In a nitrogen atmosphere, A-3 (20 g, 67.1 mmol) and [1,1'-biphenyl]-3-ylboronic acid (13.3 g, 67.1 mmol) were added to tetrahydrofuran (400 ml), stirred and refluxed. Afterwards, potassium carbonate (27.8 g, 201.4 mmol) was dissolved in water (28 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (500 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare white solid compound B-1 (16.2 g, yield 65%, MS: [M+H] ⁺ = 373.1).

Next, compound sub 3-1 was prepared.

B-1 (15 g, 40.3 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (7 g, 40.3 mmol) were added to dimethylformamide (300 ml) and stirred in a nitrogen atmosphere. and refluxed. Afterwards, potassium triphosphate (25.7 g, 120.9 mmol) was added, stirred sufficiently, and reacted for 6 hours. After cooling to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (213 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare white solid compound sub 3-1 (15.3 g, yield 72%, MS: [M+H] ⁺ = 529.2).

Next, compound sub 3-2 was prepared.

In a nitrogen atmosphere, sub 3-1 (15 g, 28.6 mmol) and bis(pinacolato)diboron (8 g, 31.4 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium acetate (8.2 g, 85.7 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.5 g, 0.9 mmol) and tricyclohexylphosphine (0.5 g, 1.7 mmol) were added. did. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (176 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethanol to prepare gray solid compound sub 3-2 (8.8 g, yield 50%, MS: [M+H] ⁺ = 618.3).

Preparation Example 4: Preparation of compound sub 4-2

First, compound C-1 was prepared.

In a nitrogen atmosphere, A-3 (20 g, 67.1 mmol) and dibenzo[b,d]furan-4-ylboronic acid (14.2 g, 67.1 mmol) were added to tetrahydrofuran (400 ml), stirred and refluxed. Afterwards, potassium carbonate (27.8 g, 201.4 mmol) was dissolved in water (28 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (518 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare white solid compound C-1 (20.2 g, yield 78%, MS: [M+H] ⁺ = 387.1).

Next, compound sub 4-1 was prepared.

C-1 (15 g, 38.9 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (6.7 g, 38.9 mmol) were added to dimethylformamide (300 ml) and stirred in a nitrogen atmosphere. and refluxed. Afterwards, potassium triphosphate (24.7 g, 116.6 mmol) was added, stirred sufficiently, reacted for 3 hours, cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (209 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare white solid compound sub 4-1 (12.6 g, yield 60%, MS: [M+H] ⁺ = 540.2).

Next, compound sub 4-2 was prepared.

In a nitrogen atmosphere, sub 4-1 (15 g, 27.8 mmol) and bis(pinacolato)diboron (7.8 g, 30.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium acetate (8 g, 83.5 mmol) was added and stirred sufficiently, and then bis(dibenzylideneacetone)palladium(0) (0.5 g, 0.8 mmol) and tricyclohexylphosphine (0.5 g, 1.7 mmol) were added. did. After reacting for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in chloroform (176 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethanol to prepare white solid compound sub 4-2 (9.8 g, yield 56%, MS: [M+H] ⁺ = 632.3).

[Example]

Example 1: Synthesis of Compound 1

Sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (4.9 g, 18.5 mmol) were added to tetrahydrofuran (200 ml) in a nitrogen atmosphere. It was added, stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (238 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 1 (7 g, yield 59%, MS: [M+H] ⁺ = 646.3).

Example 2: Synthesis of Compound 2

Sub 1-2 (10 g, 18.5 mmol) and 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine ( 6.3 g, 18.5 mmol) was added to tetrahydrofuran (200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (267 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 2 (8.4 g, yield 63%, MS: [M+H] ⁺ = 723.3).

Example 3: Synthesis of Compound 3

Sub 1-2 (10 g, 18.5 mmol) and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine ( 6.3 g, 18.5 mmol) was added to tetrahydrofuran (200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (267 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 3 (6.9 g, yield 52%, MS: [M+H] ⁺ = 723.3).

Example 4: Synthesis of Compound 4

Sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4-(naphthalen-2-yl)-6-phenyl-1,3,5-triazine (5.9 g, 18.5 mmol) were reacted with tetrazine in a nitrogen atmosphere. It was added to hydrofuran (200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (257 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 4 (7.2 g, yield 56%, MS: [M+H] ⁺ = 697.3).

Example 5: Synthesis of Compound 5

sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5-triazine (6.6) in a nitrogen atmosphere. g, 18.5 mmol) was added to tetrahydrofuran (200 ml), stirred, and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (272 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 5 (8.4 g, yield 62%, MS: [M+H] ⁺ = 737.3).

Example 6: Synthesis of Compound 6

sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (6.6) in a nitrogen atmosphere. g, 18.5 mmol) was added to tetrahydrofuran (200 ml) and stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (272 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 6 (9.8 g, yield 72%, MS: [M+H] ⁺ = 737.3).

Example 7: Synthesis of Compound 7

sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4-(dibenzo[b,d]furan-2-yl)-6-phenyl-1,3,5-triazine (6.6) in a nitrogen atmosphere. g, 18.5 mmol) was added to tetrahydrofuran (200 ml), stirred, and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (272 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 7 (10.6 g, yield 78%, MS: [M+H] ⁺ = 737.3).

Example 8: Synthesis of Compound 8

sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (6.6) in a nitrogen atmosphere. g, 18.5 mmol) was added to tetrahydrofuran (200 ml), stirred, and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (272 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound, Compound 8 (7.9 g, yield 58%, MS: [M+H] ⁺ = 737.3).

Example 9: Synthesis of Compound 9

Sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine ( 6.9 g, 18.5 mmol) was added to tetrahydrofuran (200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (278 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 9 (11 g, yield 79%, MS: [M+H] ⁺ = 753.3).

Example 10: Synthesis of Compound 10

sub 1-2 (10 g, 18.5 mmol) and 9-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (6.6 g, 18.5 mmol) in a nitrogen atmosphere. ) was added to tetrahydrofuran (200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (272 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 10 (10.7 g, yield 79%, MS: [M+H] ⁺ = 736.3).

Example 11: Synthesis of Compound 11

Sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4-phenyl-6-(phenyl-D5)-1,3,5-triazine (5 g, 18.5 mmol) were mixed with tetrahydrofuran in a nitrogen atmosphere. (200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium (0.6 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (241 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 11 (9.3 g, yield 77%, MS: [M+H] ⁺ = 652.3).

Example 12: Synthesis of Compound 12

Sub 1-2 (10 g, 18.5 mmol) and 2-chloro-4,6-bis(phenyl-D5)-1,3,5-triazine (5.1 g, 18.5 mmol) were dissolved in tetrahydrofuran (5.1 g, 18.5 mmol) in a nitrogen atmosphere. 200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.7 g, 55.4 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (243 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 12 (8.5 g, yield 70%, MS: [M+H] ⁺ = 657.3).

Example 13: Synthesis of Compound 13

Sub 2-2 (10 g, 18.4 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (4.9 g, 18.4 mmol) were added to tetrahydrofuran (200 ml) in a nitrogen atmosphere. It was added, stirred and refluxed. Afterwards, potassium carbonate (7.6 g, 55.2 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (239 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 13 (6.8 g, yield 57%, MS: [M+H] ⁺ = 649.3).

Example 14: Synthesis of Compound 14

Sub 2-2 (10 g, 18.4 mmol) and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine ( 6.3 g, 18.4 mmol) was added to tetrahydrofuran (200 ml), stirred and refluxed. Afterwards, potassium carbonate (7.6 g, 55.2 mmol) was dissolved in water (8 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (267 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 14 (7.1 g, yield 53%, MS: [M+H] ⁺ = 725.3).

Example 15: Synthesis of Compound 15

Sub 3-2 (10 g, 16.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (4.3 g, 16.2 mmol) were added to tetrahydrofuran (200 ml) in a nitrogen atmosphere. It was added, stirred and refluxed. Afterwards, potassium carbonate (6.7 g, 48.6 mmol) was dissolved in water (7 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (234 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 15 (6.6 g, yield 56%, MS: [M+H] ⁺ = 723.3).

Example 16: Synthesis of Compound 16

Sub 4-2 (10 g, 15.6 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (4.2 g, 15.6 mmol) were added to tetrahydrofuran (200 ml) in a nitrogen atmosphere. It was added, stirred and refluxed. Afterwards, potassium carbonate (6.5 g, 46.8 mmol) was dissolved in water (6 ml), stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform (230 mL), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 16 (5.9 g, yield 51%, MS: [M+H] ⁺ = 737.3).

[Experimental example]

Experimental Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1,300 Å was placed in distilled water with a detergent dissolved in it and washed with ultrasonic waves. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

The following HI-1 compound was thermally vacuum deposited to a thickness of 50 Å on the ITO transparent electrode prepared as above to form a hole injection layer. The HT-1 compound below was thermally vacuum deposited to a thickness of 250 Å on the hole injection layer to form a hole transport layer, and the HT-2 compound below was vacuum deposited to a thickness of 50 Å on the HT-1 deposition film to form an electron blocking layer. As a light emitting layer on the HT-2 deposited film, compound 1 prepared in Example 1, the YGH-1 compound below, and the phosphorescent dopant YGD-1 were co-deposited at a weight ratio of 44:44:12 to form a light emitting layer with a thickness of 400 Å.

An electron transport layer was formed by vacuum depositing the following ET-1 compound to a thickness of 250 Å on the light emitting layer, and the following ET-2 compound and Li were vacuum deposited at a weight ratio of 98:2 on the electron transport layer to form an electron injection layer with a thickness of 100 Å. formed. Aluminum was deposited to a thickness of 1000 Å on the electron injection layer to form a cathode.

In the above process, the deposition rate of organic matter was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was maintained at 1×10 ^-7 ~ 5×10 ^-8 torr. did.

<Experimental Examples 2 to 16>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1 in Example 1.

<Comparative Experimental Examples 1 to 3>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1 in Experimental Example 1. The compounds of CE1 in Table 1 below are as follows.

In the above experimental and comparative experimental examples, the voltage and efficiency of the organic light-emitting device were measured at a current density of 10 mA/cm ² , and the lifespan was measured at a current density of 50 mA/cm ² , and the results are shown in Table 1 below. . At this time, LT95 means the time when the initial luminance reaches 95%.

compound Voltage (V)
(@10mA/cm ² ) Efficiency (Cd/A)
(@10mA/cm ² ) Color coordinates
(x,y) Lifespan (h)
(LT ₉₅ at 50mA/cm ² ) Experimental Example 1 Compound 1 4.1 82.5 0.44, 0.54 347 Experimental Example 2 compound 2 4.2 83.4 0.44, 0.54 364 Experimental Example 3 Compound 3 4.3 84.4 0.44, 0.54 397 Experimental Example 4 Compound 4 4.0 80.5 0.44, 0.54 325 Experimental Example 5 Compound 5 4.0 83.4 0.44, 0.54 375 Experimental Example 6 Compound 6 4.2 81.5 0.44, 0.54 484 Experimental Example 7 Compound 7 4.0 85.4 0.44, 0.54 289 Experimental Example 8 Compound 8 3.9 79.6 0.44, 0.54 395 Experimental Example 9 Compound 9 4.3 79.7 0.44, 0.54 514 Experimental Example 10 Compound 10 4.4 79.2 0.44, 0.54 474 Experimental Example 11 Compound 11 4.1 82.7 0.44, 0.54 386 Experimental Example 12 Compound 12 4.1 82.5 0.44, 0.54 427 Experimental Example 13 Compound 13 4.1 82.5 0.44, 0.54 409 Experimental Example 14 Compound 14 4.2 85.4 0.44, 0.54 425 Experimental Example 15 Compound 15 4.2 84.4 0.44, 0.54 459 Experimental Example 16 Compound 16 4.3 83.4 0.44, 0.54 425 Comparative Experiment Example 1 CE 1 4.0 71.0 0.44, 0.54 120 Comparative Experiment Example 2 CE 2 4.1 80.8 0.44, 0.54 195 Comparative Experiment Example 3 CE 3 3.9 82.5 0.44, 0.54 215

As shown in Table 1, when the compound of the present invention was used as a light-emitting layer material, it was confirmed that it exhibited excellent efficiency and lifespan characteristics compared to the comparative experiment example. This appears to have increased electronic stability due to the substitution of triazine and carbazole groups on the dibenzofuran group, which is a core substituent. In particular, excellent properties for increasing lifespan are shown when one or more deuterium substitutions are made on additional aryl and carbazole groups. This also appears to increase electronic stability.

1: Substrate 2: Anode
3: hole transport layer 4: light emitting layer
5: Electron injection and transport layer 6: Cathode
7: hole injection layer 8: electron suppression layer
9: Hole blocking layer

Claims (10)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
Each X is independently N or CH, but two or more of the Xs are N,
Y is O or S,
L ₁ is a direct bond, or C _6-60 arylene substituted or unsubstituted with deuterium,
L ₂ is a direct bond, or C _6-60 arylene substituted or unsubstituted with deuterium,
Ar ₁ and Ar ₂ are each independently selected from the group consisting of C _6-60 aryl substituted or unsubstituted with deuterium or aryl, or N, O and S substituted or unsubstituted with deuterium or aryl. It is C _6-60 heteroaryl containing heteroatoms,
R ₁ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl,
R ₁ is unsubstituted or substituted with one or more deuterium,
R ₂ is each independently hydrogen or deuterium,
However, at least one of Ar ₁ , Ar ₂ and R ₁ is substituted with one or more deuterium, or at least one of R ₂ is deuterium,
However, the following compounds are excluded from the compounds represented by Formula 1 above.

According to paragraph 1,
L ₁ is a direct bond, phenylene, biphenylene, or naphthylene,
compound.
According to paragraph 1,
L ₂ is a direct bond or phenylene,
compound.
According to paragraph 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, naphthyl phenyl, phenanthrenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, dibenzofuranyl, or dibenzofuranyl. It is benzothiophenyl,
Ar ₁ and Ar ₂ are unsubstituted; substituted with one or more deuterium,
compound.
delete According to paragraph 1,
All Xs are N,
compound.
According to paragraph 1,
Y is O,
compound.
According to paragraph 1,
The compound represented by Formula 1 is,
Any one selected from the group consisting of the following compounds,
compound:

An organic light emitting device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers are An organic light-emitting device comprising a compound according to any one of claims 1 to 4 and 6 to 8.
According to clause 9,
The organic material layer containing the compound is a light emitting layer,
Organic light emitting device.