KR102174388B1 - Cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a cyclic compound having a novel structure and an organic light-emitting device including the same.

Description

Cyclic compound and organic light-emitting device comprising the same TECHNICAL FIELD

The present invention relates to a cyclic compound having a novel structure and an organic light emitting device including the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure made of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

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 a cyclic compound having a novel structure and an organic light emitting device including the same.

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

[Formula 1]

In Formula 1,

X ¹ to X ⁴ are each independently CR ¹ R ² , O, S or NR ³ ,

R ¹ and R ² are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,

R ³ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted O, N, Si, and S containing one or more of It is a C2-C60 heteroaryl group,

A ¹ and A ² are each a benzene ring fused with two adjacent pentagonal rings,

Y is an aromatic ring having 10 to 24 carbon atoms fused with two adjacent pentagonal rings, or a heteroaromatic ring having 10 to 24 carbon atoms including at least one of O, N, Si and S.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Formula 1 do.

The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics of the organic light-emitting device. The compound represented by Chemical Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material, and is particularly used as a light emitting material, thereby exhibiting low driving voltage and excellent efficiency. .

FIG. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
FIG. 2 shows an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it.

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

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

In this specification the term "substituted or unsubstituted" may be substituted or means a unsubstituted by R ^a, R ^a is heavy hydrogen, a halogen, a cyano group, a nitro group, an amino group, an alkyl group having 1 to 40 carbon atoms, A haloalkyl group of 1 to 40, a heteroalkyl group having 1 to 40 carbon atoms including at least one of substituted or unsubstituted O, N, Si and S, at least one of substituted or unsubstituted O, N, Si and S It may be a C 1 to C 40 heterohaloalkyl group, or a C 2 to C 40 alkenyl group including.

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

In the present specification, the alkyl group having 1 to 40 carbon atoms may be a linear, branched or cyclic alkyl group. Specifically, the alkyl group having 1 to 40 carbon atoms is a linear alkyl group having 1 to 40 carbon atoms; A linear alkyl group having 1 to 20 carbon atoms; A linear alkyl group having 1 to 10 carbon atoms; A branched or cyclic alkyl group having 3 to 40 carbon atoms; A branched or cyclic alkyl group having 3 to 20 carbon atoms; Or it may be a branched chain or cyclic alkyl group having 3 to 10 carbon atoms. More specifically, the alkyl group having 1 to 40 carbon atoms is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, It may be a neo-pentyl group or a cyclohexyl group. However, it is not limited thereto.

In the present specification, the heteroalkyl group having 1 to 40 carbon atoms may be one in which one or more carbons of the alkyl group are each independently substituted with O, N, Si, or S. For example, as an example of a straight-chain alkyl group, the heteroalkyl group in which carbon 1 of the n-butyl group is substituted with O is an n-propoxy group, the heteroalkyl group substituted with N is an n-propylamino group, and the heteroalkyl group substituted with Si is n -Propylsilyl group, and the heteroalkyl group substituted with S is an n-propylthio group. And, as an example of a branched chain alkyl group, the heteroalkyl group in which carbon 1 of the neo-pentyl group is substituted with O is a t-butoxy group, the heteroalkyl group substituted with N is a t-butylamino group, and the heteroalkyl group substituted with Si is t -Butylsilyl group, and the heteroalkyl group substituted with S is a t-butylthio group. In addition, as an example of a cyclic alkyl group, the heteroalkyl group in which carbon 2 of the cyclohexyl group is substituted with O is a 2-tetrahydropyranyl group, and the heteroalkyl group substituted with N is a 2-piperidinyl group, The heteroalkyl group substituted with Si is a 1-sila-cyclohexyl group, and the heteroalkyl group substituted with S is a 2-tetrahydrothiopyranyl group. Specifically, the C1-C40 heteroalkyl group is a C1-C40 linear, branched or cyclic hydroxyalkyl group; A linear, branched or cyclic alkoxy group having 1 to 40 carbon atoms; A straight chain, branched chain or cyclic alkoxyalkyl group having 2 to 40 carbon atoms; A linear, branched or cyclic aminoalkyl group having 1 to 40 carbon atoms; A linear, branched or cyclic alkylamino group having 1 to 40 carbon atoms; A linear, branched or cyclic alkylaminoalkyl group having 1 to 40 carbon atoms; A linear, branched or cyclic silylalkyl (oxy) group having 1 to 40 carbon atoms; A linear, branched or cyclic alkyl (oxy)silyl group having 1 to 40 carbon atoms; A linear, branched or cyclic alkyl (oxy) silyl alkyl (oxy) group having 1 to 40 carbon atoms; A straight chain, branched chain or cyclic mercaptoalkyl group having 1 to 40 carbon atoms; A linear, branched or cyclic alkylthio group having 1 to 40 carbon atoms; Or it may be a C2-C40 linear, branched or cyclic alkylthioalkyl group. More specifically, the heteroalkyl group having 1 to 40 carbon atoms is a hydroxymethyl group, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a t-butoxy group, a cyclohexanoxy group, a methoxymethyl group, iso-pro Foxymethyl group, cyclohectoxymethyl group, 2-tetrahydropyranyl group, aminomethyl group, methylamino group, n-propylamino group, t-butylamino group, methylaminopropyl group, 2-piperidinyl group, n- Propylsilyl group, trimethylsilyl group, dimethylmethoxysilyl group, t-butylsilyl group, 1-sila-cyclohexyl group, n-propylthio group, t-butylthio group or 2-tetra Hydrothiopyranyl (2-tetrahydrothiopyranyl) group, etc. are mentioned. However, it is not limited thereto.

In the present specification, the alkenyl group having 2 to 40 carbon atoms may be a linear, branched or cyclic alkenyl group. Specifically, the alkenyl group having 2 to 40 carbon atoms is a linear alkenyl group having 2 to 40 carbon atoms; A linear alkenyl group having 2 to 20 carbon atoms; A linear alkenyl group having 2 to 10 carbon atoms; A branched alkenyl group having 3 to 40 carbon atoms; A branched alkenyl group having 3 to 20 carbon atoms; A branched alkenyl group having 3 to 10 carbon atoms; A cyclic alkenyl group having 5 to 40 carbon atoms; A cyclic alkenyl group having 5 to 20 carbon atoms; Or it may be a cyclic alkenyl group having 5 to 10 carbon atoms. More specifically, the alkenyl group having 2 to 40 carbon atoms may be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, or a cyclohexenyl group. However, it is not limited thereto.

In the present specification, the aryl group having 6 to 60 carbon atoms may be a monocyclic aryl group or a polycyclic aryl group. Specifically, the aryl group having 6 to 60 carbon atoms is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or it may be a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms. More specifically, the aryl group having 6 to 60 carbon atoms may be a phenyl group, a biphenyl group, or a terphenyl group as a monocyclic aryl group, and a naphthyl group, anthracenyl group, phenanthryl group, triphenylenyl group, pyrethyl group as a polycyclic aryl group It may be a nil group, a perylenyl group, a chrysenyl group, or a fluorenyl group. However, it is not limited thereto.

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

Etc. However, it is not limited thereto.

In the present specification, the heteroaryl group having 2 to 60 carbon atoms may be one in which one or more carbons of the aryl group are each independently substituted with O, N, Si, or S. For example, a heteroaryl group in which carbon 9 of a fluorenyl group is substituted with O is a dibenzofuranyl group, a heteroaryl group substituted with N is a carbazoli group, and a heteroaryl group substituted with Si is a 9-sila-fluororenyl group The heteroaryl group substituted with S is a dibenzothiophenyl group. Specifically, the heteroaryl group having 2 to 60 carbon atoms is a heteroaryl group having 2 to 30 carbon atoms; Or it may be a C2 to C20 heteroaryl group. More specifically, the heteroaryl group having 2 to 60 carbon atoms is a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, Triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyra Genyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group ), thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but are not limited thereto.

In Formula 1, A ¹ and A ² are each a benzene ring fused with two adjacent pentagonal rings, and Y is an aromatic ring or heteroaromatic ring fused with two adjacent pentagonal rings. In Formula 1, the four pentagonal rings are described so that X ¹ to X ⁴ are all upward, but the arrangement of the four pentagonal rings is not limited by this description.

)은 하기와 같이 6 가지 종류의 연결 구조를 형성할 수 있다. For example, A ¹ (

) Can form six types of connection structures as follows.

In Formula 1, Y may be naphthalene, phenanthrene, pyrene, or triphenylene.

Specifically, the compound represented by Formula 1 may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, X ¹ , X ⁴ , A ¹ , A ² and R ³ are the same as those of Formula 1.

More specifically, the compound represented by Formula 1 may be selected from the group consisting of compounds represented by the following Formulas 3 to 8.

[Formula 3] [Formula 4]

[Formula 5] [Formula 6]

[Formula 7] [Formula 8]

In Formulas 3 to 8, X ¹ to X ⁴ are the same as those of Formula 1.

When at least one of X ¹ to X ⁴ in Formula 1 is CR ¹ R ² , R ¹ and R ² may each independently be a methyl group, an ethyl group, a propyl group, or a butyl group. More specifically, R ¹ and R ² may be a methyl group.

When at least one of X ¹ to X ⁴ in Formula 1 is NR ³ R ³ is a methyl group, ethyl group, propyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, triphenylenyl group, or dibenzofur It may be a ranil group. More specifically, R ³ may be an ethyl group, a phenyl group, a biphenyl group, or a dibenzofuranyl group.

In Formula 1, X ¹ may be the same as X ⁴ and X ² may be the same as X ³ .

And, X ² and X ³ may be NR ³ .

The compound represented by Formula 1 may be selected from the group consisting of the following compounds.

The compound represented by Chemical Formula 1 can be prepared by a manufacturing method as shown in Scheme 1 below.

[Scheme 1]

Specifically, compound A can be synthesized from a starting material (S.M.) through a Suzuki reaction. Then, compound B can be synthesized from compound A by intramolecular amination using CuI. In addition, a compound represented by Formula 1 may be synthesized by substituting hydrogen of the amine of Compound B with a desired substituent. As a non-limiting example, formula C can be synthesized from compound B through the Buchwald reaction. The manufacturing method may be more specific in the manufacturing examples described later.

In addition, the present invention provides an organic light-emitting device including the compound represented by Chemical Formula 1. For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Formula 1 to provide.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number of organic material layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. It may contain a compound to be displayed.

In addition, the organic material layer may include an emission layer, and the emission layer may include a compound represented by Formula 1 above.

In addition, the organic material layer may include an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons is represented by Formula 1 above. It may contain a compound to be displayed.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. 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.

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

FIG. 2 shows an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the emission layer, and the electron transport layer.

The organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, 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 may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or alloy thereof is deposited on the substrate to form an anode. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

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

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

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SNO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

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

The hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, etc., but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer.As a hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the emission layer and having high mobility for holes This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.

The compound represented by Formula 1 may be used in the emission layer. In particular, the compound represented by Chemical Formula 1 is used as a blue dopant, thereby lowering the driving voltage of the organic electronic device and improving the efficiency, thereby remarkably improving the consumption strategy.

In addition to this, the light-emitting layer may include other light-emitting materials known in the art to which the present invention belongs. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. 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, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted A compound in which at least one arylvinyl group is substituted on the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

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

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect to the light emitting layer or light emitting material, and injects holes of excitons generated from the light emitting layer A compound that prevents migration to the layer and has excellent thin film formation ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

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

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

Preparation of the compound represented by Formula 1 and an organic light emitting device including the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Synthesis example 1: Synthesis of cyclic compounds

1) Preparation of compound A

Compound SM1 (40 g, 126 mmol), Compound SM2 (72.4 g, 265 mmol), K ₂ CO ₃ (52.2 g, 378 mmol), Pd(PPh ₃ ) ₄ (4.4 g, 3.8 mmol), THF (400 mL ), H ₂ O (100 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction product was cooled to room temperature, the water layer was removed, and the organic layer was concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound A (30.1 g, 39% yield) (MS: [M+H] ⁺ =612).

2) Preparation of compound B

Compound A (30.1 g, 49.2 mmol), CuI (9.4 g, 49.2 mmol), Cs ₂ CO ₃ (32.1 g, 98.4 mmol), and DMF (500 mL) were mixed, followed by stirring and refluxing for 24 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound B (7.7 g, 29% yield) (MS: [M+H] ⁺ =539).

3) Preparation of compound 1

Compound B (7.7 g, 14.3 mmol), bromobenzene (4.5 g, 28.6 mmol), sodium-tertiary-butoxide (NaOt-Bu, 5.0 g, 51.9 mmol) and Pd[P(t-Bu) ₃ ] ₂ ( 146 mg, 2 mol%) was suspended in toluene (200 mL). The resulting mixture was stirred and refluxed for about 6 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound 1 (6.5 g, 66% yield) (MS: [M+H] ⁺ =691).

Synthesis example 2: Synthesis of cyclic compounds

1) Preparation of compound C

Compound B (15 g, 27.8 mmol), bromobenzene (4.4 g, 25.9 mmol), sodium-tertiary-butoxide (NaOt-Bu, 5.0 g, 51.9 mmol) and Pd[P(t-Bu) ₃ ] ₂ ( 284 mg, 2 mol%) was suspended in toluene (200 mL). The resulting mixture was stirred and refluxed for about 6 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound C (5.5 g, 32% yield) (MS: [M+H] ⁺ =615).

2) Preparation of compound 2

A mixture of compound C (5.5 g, 8.9 mmol), diethylsulfate (2.8 g, 17.9 mmol), Cs ₂ CO ₃ (5.8 g, 17.9 mmol), and DMF (50 mL) was stirred at 80 for 48 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound 2 (3.5 g, 61% yield) (MS: [M+H] ⁺ =643).

Synthesis example 3: Synthesis of cyclic compounds

1) Preparation of compound D

Compound SM1 (40 g, 126 mmol), Compound SM2 (65.3 g, 265 mmol), K ₂ CO ₃ (52.2 g, 378 mmol), Pd(PPh ₃ ) ₄ (4.4 g, 3.8 mmol), THF (400 mL ), H ₂ O (100 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction product was cooled to room temperature, the water layer was removed, and the organic layer was concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound D (16.2 g, 23% yield) (MS: [M+H] ⁺ =560).

2) Preparation of compound E

Compound D (16.2 g, 29.0 mmol), CuI (5.5 g, 29.0 mmol), Cs ₂ CO ₃ (18.9 g, 58.0 mmol), and DMF (300 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound E (3.2 g, 23% yield) (MS: [M+H] ⁺ =487).

3) Preparation of compound 3

Compound E (3.2 g, 6.7 mmol), bromobenzene (2.6 g, 16.7 mmol), sodium-tertiary-butoxide (NaOt-Bu, 1.9 g, 20.1 mmol) and Pd[P(t-Bu) ₃ ] ₂ ( 68 mg, 2 mol%) was suspended in toluene (200 mL). The resulting mixture was stirred and refluxed for about 6 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound 3 (3.0 g, 71% yield) (MS: [M+H] ⁺ =639).

Synthesis example 4: Synthesis of cyclic compounds

1) Preparation of compound F

Compound SM1 (40 g, 126 mmol), Compound SM2 (65.3 g, 265 mmol), K ₂ CO ₃ (52.2 g, 378 mmol), Pd(PPh ₃ ) ₄ (4.4 g, 3.8 mmol), THF (400 mL ), H ₂ O (100 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction product was cooled to room temperature, the water layer was removed, and the organic layer was concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound F (17.6 g, 25% yield) (MS: [M+H] ⁺ =560).

2) Preparation of compound G

Compound F (17.6 g, 31.5 mmol), CuI (6.0 g, 31.5 mmol), Cs ₂ CO ₃ (20.5 g, 63.0 mmol), and DMF (300 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound G (3.8 g, 25% yield) (MS: [M+H] ⁺ =487).

3) Preparation of compound 4

Compound G (3.8 g, 7.8 mmol), bromobenzene (3.1 g, 19.5 mmol), sodium-tertiary-butoxide (NaOt-Bu, 1.9 g, 20.1 mmol) and Pd[P(t-Bu) ₃ ] ₂ ( 68 mg, 2 mol%) was suspended in toluene (200 mL). The resulting mixture was stirred and refluxed for about 6 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound 4 (3.6 g, 73% yield) (MS: [M+H] ⁺ =639).

Synthesis example 5: Synthesis of cyclic compounds

1) Preparation of compound H

Compound SM1 (40 g, 127 mmol), Compound SM2 (69.0 g, 253 mmol), K ₂ CO ₃ (70.2 g, 508 mmol), Pd(PPh ₃ ) ₄ (1.46 g, 1.27 mmol), THF (400 mL ), H ₂ O (100 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction product was cooled to room temperature, the water layer was removed, and the organic layer was concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound H (32.6 g, 42% yield) (MS: [M+H] ⁺ =611).

2) Preparation of compound I

Compound H (32.6 g, 53.3 mmol), CuI (10.1 g, 53.3 mmol), Cs ₂ CO ₃ (34.7 g, 106.6 mmol), DMF (500 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound I (9.9 g, 32% yield) (MS: [M+H] ⁺ =539).

3) Preparation of compound 5

Compound I (9.9 g, 17.1 mmol), bromobenzene (6.7 g, 42.7 mmol), sodium-tertiary-butoxide (NaOt-Bu, 5.0 g, 51.9 mmol) and Pd[P(t-Bu) ₃ ] ₂ ( 175 mg, 2 mol%) was suspended in toluene (200 mL). The resulting mixture was stirred and refluxed for about 6 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound 5 (7.4 g, 59% yield) (MS: [M+H] ⁺ =691).

Synthesis example 6: Synthesis of cyclic compounds

1) Preparation of compound J

Compound SM1 (40 g, 126 mmol), Compound SM2 (65.3 g, 265 mmol), K ₂ CO ₃ (52.2 g, 378 mmol), Pd(PPh ₃ ) ₄ (4.4 g, 3.8 mmol), THF (400 mL ), H ₂ O (100 mL) were mixed, stirred and refluxed for 24 hours. After completion of the reaction, the reaction product was cooled to room temperature, the water layer was removed, and the organic layer was concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound J (19.7 g, 28% yield) (MS: [M+H] ⁺ =560).

2) Preparation of compound K

Compound J (19.7 g, 35.2 mmol), CuI (6.7 g, 35.2 mmol), Cs ₂ CO ₃ (22.9 g, 70.4 mmol), and DMF (300 mL) were mixed, followed by stirring and refluxing for 24 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound K (3.4 g, 20% yield) (MS: [M+H] ⁺ =487).

3) Preparation of compound 6

Compound K (3.4 g, 7.0 mmol), bromobenzene (2.7 g, 17.5 mmol), sodium-tertiary-butoxide (NaOt-Bu, 1.9 g, 20.1 mmol) and Pd[P(t-Bu) ₃ ] ₂ ( 72 mg, 2 mol%) was suspended in toluene (200 mL). The resulting mixture was stirred and refluxed for about 6 hours. After completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrated residue was purified by silica gel column chromatography (eluent: THF/Hex) to obtain compound 6 (3.1 g, 70% yield) (MS: [M+H] ⁺ =639).

Example 1: Fabrication of an organic light emitting device

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) to a thickness of 1000 Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered using a filter made by Millipore Co. was used as distilled water. After washing the ITO substrate for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, the ITO substrate was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Then, the ITO substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the prepared ITO electrode, hexanitrile hexaazatriphenylene (HAT) was thermally vacuum deposited to a thickness of 100 Å to form a hole injection layer. On the hole injection layer, 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) was thermally vacuum deposited to a thickness of 1100 Å to form a hole transport layer. On the hole transport layer, BH shown below and Compound 1 (blue dopant) prepared in Synthesis Example 1 were mixed at a weight ratio of 25:1 and thermally vacuum deposited to a thickness of 300 Å to form a light emitting layer. On the light emitting layer, ET-A and LiQ (Lithium Quinalate) shown below were mixed at a weight ratio of 1:1 and thermally vacuum deposited to a thickness of 300 Å to form an electron injection and transport layer.

HAT NPB BH

ET- A LiQ

Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 2,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2 X 10 ^An organic light emitting device was manufactured by maintaining ^-7 to 5 X 10 ^-6 torr.

Example 2: Fabrication of an organic light emitting device

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 2 prepared in Synthesis Example 2 was used instead of Compound 1 in Example 1 above.

Example 3: Fabrication of an organic light emitting device

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 3 prepared in Synthesis Example 3 was used instead of Compound 1 in Example 1.

Example 4: Fabrication of an organic light emitting device

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 4 prepared in Synthesis Example 4 was used instead of Compound 1 in Example 1.

Example 5: Fabrication of organic light emitting device

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 5 prepared in Synthesis Example 5 was used instead of Compound 1 in Example 1.

Example 6: Fabrication of organic light emitting device

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 6 prepared in Synthesis Example 6 was used instead of Compound 1 in Example 1.

Comparative example 1: Fabrication of an organic light emitting device

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of Formula BD1 was used instead of Compound 1 in Example 1.

BD1

Test example : Performance evaluation of organic light emitting device

Voltage and efficiency were measured when a current (10 mA/cm ² ) was applied to the organic light emitting device fabricated in the above Examples and Comparative Examples, and the Commission Internationale de I'Eclairage (CIE) color coordinate was applied to the voltage 11 V, current density. 34.5 mA/cm ² , luminance 5,731 cd/m ² , maximum current efficiency 34.8 cd/A, maximum power efficiency 21.6 lm/W, and quantum efficiency 15.6% were measured and shown in Table 1 below.

Cyclic compound
(blue dopant) Voltage [Unit: V] Efficiency [Unit: cd/A] Color coordinates (x, y) Example 1 Compound 1 3.91 6.65 (0.141, 0.053) Example 2 Compound 2 3.99 6.60 (0.142, 0.051) Example 3 Compound 3 4.20 5.81 (0.140, 0.050) Example 4 Compound 4 3.99 6.03 (0.140, 0.050) Example 5 Compound 5 3.98 6.01 (0.141, 0.051) Example 6 Compound 6 4.16 5.97 (0.140, 0.052) Comparative Example 1 BD1 4.86 0.59 (0.144, 0.057)

From the results of Table 1, the cyclic compound having a novel structure according to an embodiment of the present invention can be used as a material for a light emitting layer of organic electronic devices including organic light emitting devices, and organic electronic devices including organic light emitting devices using the same It is confirmed that the efficiency, driving voltage, and stability are shown. In particular, the cyclic compound having a novel structure according to an embodiment of the present invention is used as a blue dopant of an organic light-emitting device, thereby lowering the driving voltage of the organic light-emitting device and inducing an increase in efficiency, thereby improving power consumption. have.

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

Claims (11)

Compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X ¹ and X ⁴ are the same and are CR ¹ R ² , O, S or NR ³ ,
X ² and X ³ are NR ³ ,
R ¹ and R ² are each independently a methyl group, an ethyl group, a propyl group, or a butyl group,
R ³ is a methyl group, ethyl group, propyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, triphenylenyl group or dibenzofuranyl group,
A ¹ and A ² are each a benzene ring fused with two adjacent pentagonal rings,
Y is naphthalene fused with two adjacent pentagonal rings.
delete The compound of claim 1, wherein the compound represented by Formula 1 is represented by the compound represented by Formula 2 below:
[Formula 2]

In Formula 2, X ¹ , X ⁴ , A ¹ , A ² and R ³ are the same as those of Formula 1.
The compound of claim 1, wherein the compound represented by Formula 1 is selected from the group consisting of compounds represented by the following Formulas 3 to 8:
[Formula 3] [Formula 4]

[Formula 5] [Formula 6]

[Formula 7] [Formula 8]

In Formulas 3 to 8, X ¹ to X ⁴ are the same as those of Formula 1.
delete delete delete delete The compound of claim 1, wherein the compound represented by Formula 1 is selected from the group consisting of the following compounds:

.
A first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound of claim 1.
The organic light-emitting device of claim 10, wherein the organic material layer containing the compound is a light-emitting layer.

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