KR20180063710A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by the following formula (I). If the organic light emitting compound is adopted as an electron transport material of an electron transport layer, an organic light emitting device with high quantum efficiency and high luminous efficiency can be implemented.

Description

TECHNICAL FIELD The present invention relates to an organic electroluminescent compound and an electroluminescent device comprising the same,

TECHNICAL FIELD The present invention relates to an organic light emitting compound, and more particularly, to an organic light emitting device employing an organic light emitting compound employed in an electron transporting layer of an organic electroluminescent device, and an organic electroluminescent device using the same to remarkably improve light emitting properties such as luminous efficiency and quantum efficiency.

The organic electroluminescent device can not only form an element on a transparent substrate but also can operate at a low voltage of 10 V or less as compared with a plasma display panel (Plasma Display Panel) or an inorganic electroluminescence (EL) display, It has the advantage of excellent color and has three colors of green, blue, and red. It has recently become a subject of interest as a next generation display device.

However, in order for such an organic electroluminescent device to exhibit such characteristics, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material, which are materials forming an organic layer in a device, However, until now, stable and efficient development of an organic material layer material for an organic electroluminescence device has not been sufficiently achieved. Therefore, development of a new material capable of improving luminescence characteristics and development of an organic layer structure in a device are continuously required.

Accordingly, it is an object of the present invention to provide a novel organic light emitting compound and an organic electroluminescent device including the same, which can be used in an electron transporting layer in an organic electroluminescent device to significantly improve light emitting efficiency.

Further, it is an object of the present invention to provide an organic electroluminescent device in which quantum efficiency and luminous efficiency can be remarkably improved by employing a novel organic luminescent compound together with a conventional electron transporting material by using the electron transporting layer as a plurality of layers.

In order to solve the above problems, the present invention provides an organic electroluminescent compound represented by the following formula (I) and an organic electroluminescent device comprising the same.

(I)

The specific structure and substituent of the above-mentioned formula (I) will be described later.

The organic electroluminescent device employing the organic luminescent compound according to the present invention in the electron transport layer can realize significantly improved luminescent efficiency as compared with the device employing the conventional electron transporting material and can be usefully used in various display devices.

1 to 5 are cross-sectional views illustrating the structure of an organic electroluminescent device according to an embodiment of the present invention.

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

The present invention relates to an organic electroluminescent device having an organic electroluminescent compound represented by the following formula (I) and having excellent quantum efficiency and luminous efficiency when used as an electron transporting material in an organic layer in an organic electroluminescent device.

(I)

In the above formula (I)

X ₁ is any one selected from S, O, CR ₁ R ₂ and SiR ₃ R ₄ ; X ₂ to X ₄ are the same or different from each other, and each independently CR ₅ or N;

Wherein R ₁ to R ₅ are the same or different and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted 3-carbon group To 30, and R ₁ to R ₅ may be connected to each other or adjacent substituents to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.

L ₁ to L ₃ are each independently a direct bond or a substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group.

Ar ₁ to Ar ₂ are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted C3- A substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl, and a substituted or unsubstituted C 3 -C 30 hetero An aryl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazole group.

In the present invention, the substituted or unsubstituted alkyl group may be substituted with at least one substituent selected from the group consisting of hydrogen, a halogen group, a nitro group, a hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group and a heterocyclic group Means that at least two of the substituents in the substituent are substituted with a substituent to which they are linked, or have no substituent.

Specific examples of the substituted arylene group include a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group and a tetracenyl group. Anthracenyl group and the like are substituted with other substituents.

The substituted heteroarylene group includes a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group and condensed heterocyclic groups thereof such as a benzquinoline group, A benzimidazole group, a benzimidazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzzcarbazole group, a dibenzothiophenyl group, a dibenzofurane group and the like are substituted with other substituents.

In the present invention, examples of the substituents will be specifically described below, but the present invention is not limited thereto.

In the present invention, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, Ethyl, propyl, isopropyl, n-butyl, isobutyl, isobutyl, isobutyl, A tert-butyl group, a tert-butyl group, a 2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, Ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group and the like, but are not limited thereto.

In the present invention, the alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 to 20, which does not cause steric hindrance. Specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an i-propyloxy group, a n-butoxy group, an isobutoxy group, a tert- , Neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n- , A benzyloxy group, a p-methylbenzyloxy group, and the like, but are not limited thereto.

In the present invention, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20. Specific examples include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-yl group, But are not limited to, - (naphthyl-1-yl) vinyl-1-yl group, 2,2-bis (diphenyl-1-yl) vinyl-1-yl group, stilbenyl group, styrenyl group and the like.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, , A chlorenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluororanthrene group, but the scope of the present invention is not limited to these examples.

In the present invention, the heterocyclic group is a hetero ring group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl 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, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, , An indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a dibenzofurancyl group, a phenanthroline group, An isothiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group and the like, but is not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically includes cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, Methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo An octyl group, and the like, but are not limited thereto.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

,

등이 있다.In the present invention, a fluorenyl group is a structure in which two cyclic organic compounds are connected via one atom,

,

.

,

등이 있다.In the present invention, a fluorenyl group includes a structure of an open fluorenyl group, wherein an open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected via one atom For example,

,

.

The organic luminescent compound according to the present invention represented by the above formula (I) can be used as an organic material layer of an organic light emitting diode due to its structural specificity, and more specifically, as an electron transport layer material of an organic material layer.

Preferred examples of the compound represented by the formula (I) according to the present invention include, but are not limited to, the following compounds.

An organic luminescent compound having the intrinsic characteristics of the substituent introduced by introducing various substituents into the core structure having the above structure can be synthesized. For example, by introducing a substituent used in a hole injection layer material, a hole transport layer material, a light emitting layer material, and an electron transport layer material used in the production of an organic electroluminescent device into the structure, a material meeting the requirements of each organic layer can be manufactured Particularly, when the compound of the formula (I) according to the present invention is used alone as an electron transporting layer material or after designing a plurality of electron transporting layers as a plurality of electron transporting layers together with a conventional electron transporting layer material, The luminous efficiency and the life characteristic can be further improved.

The organic luminescent compound according to the present invention can be applied to an organic electroluminescent device according to a conventional production method.

The organic electroluminescent device according to one embodiment of the present invention may have a structure including a first electrode, a second electrode and an organic material layer disposed therebetween, and the organic electroluminescent compound according to the present invention may be used for an organic material layer And can be manufactured using conventional device manufacturing methods and materials.

The organic material layer of the organic electroluminescent device according to 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, a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. However, it is not so limited and may include fewer or greater numbers of organic layers.

Therefore, in the organic electroluminescent device according to the present invention, the organic material layer may include at least one of an electron injection layer, an electron transport layer, and layers simultaneously performing electron injection and electron transport, May include organic luminescent compounds represented by Formula (I).

For example, the structure of an organic electronic device according to the present invention is illustrated in Figs.

1 shows an organic electroluminescent device 1 in which an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5, an electron transporting layer 6 and a cathode 7 are sequentially laminated on a substrate 1 Are illustrated. In such a structure, the compound represented by Formula (I) may be included in the hole injection layer (3), the hole transport layer (4), the light emitting layer (5), or the electron transport layer (6) (6) may comprise a first electron transporting layer and a second electron transporting layer, the second electron transporting layer may comprise a conventional electron transporting compound, and the first electron transporting layer may comprise a compound represented by the above formula (I).

2 shows the structure of an organic electroluminescent device in which an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5 and a cathode 7 are sequentially laminated on a substrate 1 . In this structure, the compound represented by the formula (I) may be contained in the hole injection layer (3), the hole transport layer (4) or the electron transport layer (6) 1 electron transporting layer and a second electron transporting layer, the second electron transporting layer may comprise a conventional electron transporting compound, and the first electron transporting layer may comprise a compound represented by the above formula (I).

3 shows a structure of an organic electroluminescent device in which an anode 2, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6 and a cathode 7 are sequentially stacked on a substrate 1 have. In this structure, the compound represented by Formula (I) may be included in the hole transport layer (4), the light emitting layer (5), or the electron transport layer (6) Transporting layer and a second electron transporting layer, the second electron transporting layer may comprise a conventional electron transporting compound, and the first electron transporting layer may comprise a compound represented by the above formula (I).

4 shows a structure of an organic electroluminescent device in which an anode 2, a light emitting layer 5, an electron transport layer 6 and a cathode 7 are sequentially laminated on a substrate 1. In FIG. In this structure, the compound represented by the formula (I) may be included in the light emitting layer (5) or the electron transport layer (6). Particularly, the electron transport layer (6) The second electron transporting layer may comprise a conventional electron transporting compound, and the first electron transporting layer may comprise a compound represented by the above formula (I).

5 illustrates a structure of an organic electroluminescent device in which an anode 2, a light emitting layer 5, and a cathode 7 are sequentially laminated on a substrate 1. In FIG. In such a structure, the compound represented by Formula (I) may be included in the light emitting layer (5).

According to a preferred embodiment of the present invention, the compound represented by the formula (I) may be contained in the electron transport layer (6).

For example, the organic electroluminescent device according to the present invention can be manufactured by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form a metal oxide or a conductive metal oxide on the substrate, An anode is formed by depositing an alloy on the anode, and an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer is formed on the anode, and then a substance usable as a cathode is deposited thereon.

In addition to such a method, an organic electroluminescent device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) metal oxides, ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT) , Conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or an alloy thereof; a multilayer such as LiF / Al or LiO ₂ / Structural materials, and the like, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazol-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and A benzimidazole-based compound, a poly (p-phenylene vinylene) (PPV) -based polymer, a spiro compound, polyfluorene, rubrene, and the like.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is highly mobile, is suitable. Specifically, it may be an organic light-emitting compound represented by Formula (I) according to the present invention, or may be an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, a hydroxyflavone-metal complex, . According to a preferred embodiment of the present invention, a plurality of layers comprising a first electron transporting layer comprising the above-mentioned conventional electron transporting material and an organic light emitting compound represented by the following formula Can be designed.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

In addition, the organic electroluminescent compound according to the present invention can act on a principle similar to that applied to an organic electroluminescent device in an organic electronic device including an organic solar cell, an organophotoreceptor, an organic transistor and the like.

Hereinafter, synthesis examples and device embodiments of preferred compounds are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthetic example  1: Synthesis of compound 1

(One) Manufacturing example  1: Synthesis of intermediate 1-1

1,8-Dibromo-9,9-dimethyl- 9H-fluorene (30 g, 0.085 mol, Yurui), phenylboronic acid (10.36 g, 0.085 mol, sigma aldrich), Pd (PPh 3) 4 (3.93 g, 0.0034 mol , sigma aldrich), K ₂ CO ₃ (20.04 g, 0.145 mol, Sigma aldrich) and 300 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and purified by column (n-hexane: MC) to obtain <Intermediate 1-1> (23.75 g, yield 80%). (m / z = 349)

(2) Manufacturing example  2: Synthesis of intermediate 1-2

PdCl ₂ (dppf) (1.98 g, 0.0027 mol, Sigma Aldrich), KOAc (13.35 g, 0.136 mmol), bis (pinacolate) diboron (20.82 g, 0.082 mol, mol, Sigma aldrich), and the mixture was reacted at 95 ° C for 24 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and column-purified (n-hexane: MC) to obtain 18.87 g (yield 70%) of Intermediate 1-2. (m / z = 396)

(3) Manufacturing example  3: Synthesis of intermediate 1-3

Intermediate 1-2 (18.87 g, 0.048 mol) , 2,4,6-trichloro-1,3,5-triazine (8.85 g, 0.048 mol, sigma aldrich), Pd (PPh 3) 4 (2.20 g, 0.0019 mol , sigma aldrich), K ₂ CO ₃ (11.33 g, 0.082 mol, sigma aldrich) and 200 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and purified by column (n-hexane: MC) to obtain 15.06 g (yield 75%) of Intermediate 1-3. (m / z = 418)

(4) Manufacturing example  4: Synthesis of intermediate 1-4

Intermediate 1-3 (15.06 g, 0.036 mol) , biphenyl-4-ylboronic acid (7.13 g, 0.036 mol, sigma aldrich), Pd (PPh 3) 4 (1.62 g, 0.0014 mol, sigma aldrich), K 2 CO 3 (8.43 g, 0.061 mol, Sigma aldrich) and 150 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 14.47 g (yield 75%) of Intermediate 1-4. (m / z = 536)

(5) Manufacturing example  5: Synthesis of Compound 1

Intermediate 1-4 (14.47 g, 0.027 mol) , phenylboronic acid (3.29 g, 0.027 mol, sigma aldrich), Pd (PPh 3) 4 (1.27 g, 0.0011 mol, sigma aldrich), K 2 CO 3 (6.36 g, 0.046 mol, Sigma aldrich) and 100 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 12.48 g (yield 80%) of <Compound 1>.

(M, 4H), 7.53-7.41 (m, 17H), 7.25 (d, 2H), 1.72 (s, 6H)

LC / MS: m / z = 578 [(M + 1) ^&lt; ^{+ &}

Synthetic example  2: Compound 36 Synthesis

(One) Manufacturing example  1: Synthesis of Intermediate 36-1

4,6-Dibromodibenzo [b, d] furan (30 g, 0.092 mol, Yurui), phenylboronic acid (11.22 g, 0.092 mol, sigma aldrich), Pd (PPh 3) 4 (4.28 g, 0.0037 mol, sigma aldrich) , K ₂ CO ₃ (21.56 g, 0.156 mol, sigma aldrich) and 300 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and column-purified (n-hexane: MC) to obtain 23.79 g (yield 80%) of Intermediate 36-1. (m / z = 323)

(2) Manufacturing example  2: Synthesis of intermediate 36-2

Intermediate 36-1 (23.79 g, 0.074 mol) , 1,4-phenylenediboronic acid (12.27 g, 0.074 mol, sigma aldrich), Pd (PPh 3) 4 (3.47 g, 0.0030 mol, sigma aldrich), K 2 CO 3 (17.41 g, 0.126 mol, Sigma aldrich) and 250 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to give 20.21 g (yield 75%) of Intermediate 36-2. (m / z = 364)

(3) Manufacturing example  3: Synthesis of intermediate 36-3

Intermediate 36-2 (20.21 g, 0.056 mol) , 2,4,6-trichloro-1,3,5-triazine (10.33 g, 0.056 mol, sigma aldrich), Pd (PPh 3) 4 (2.54 g, 0.0022 mol , Sigma aldrich), K ₂ CO ₃ (13.13 g, 0.095 mol, Sigma aldrich) and 200 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 19.67 g (yield 75%) of Intermediate 36-3. (m / z = 468)

(4) Manufacturing example  4: Synthesis of intermediate 36-4

Intermediate 36-3 (19.67 g, 0.042 mol) , biphenyl-4-ylboronic acid (8.32 g, 0.042 mol, sigma aldrich), Pd (PPh 3) 4 (1.96 g, 0.0017 mol, sigma aldrich), K 2 CO 3 (9.81 g, 0.071 mol, Sigma aldrich) and 150 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and column-purified (n-hexane: MC) to obtain 18.46 g (yield: 75%) of Intermediate 36-4. (m / z = 586)

(5) Manufacturing example  5: Synthesis of Compound 36

Intermediate 2-4 (18.46 g, 0.032 mol) , 9,9-dimethyl-9H-fluoren-1-ylboronic acid (7.62 g, 0.032 mol, yurui), Pd (PPh 3) 4 (1.50 g, 0.0013 mol, sigma aldrich), K ₂ CO ₃ (7.46 g, 0.054 mol, Sigma aldrich) and 100 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 19.04 g (yield 80%) of Compound 36.

(M, 10H), 7.55-7.38 (m, 16H), 7.28-7.25 (m, 5H), 1.72 (s, 6H)

LC / MS: m / z = 744 [(M + 1) ^&lt; ^{+ &}

Synthetic example  3: Compound 51 Synthesis

(One) Manufacturing example  1: Synthesis of Compound 51

Intermediate 36-4 (18.46 g, 0.032 mol) , biphenyl-2-ylboronic acid (6.34 g, 0.032 mol, sigma aldrich), Pd (PPh 3) 4 (1.50 g, 0.0013 mol, sigma aldrich), K 2 CO 3 (7.46 g, 0.054 mol, Sigma aldrich) and 100 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 18.02 g (yield 80%) of Compound 51.

7.85 (m, 12H), 7.52-7.38 (m, 17H), 7.25 (d, 4H)

LC / MS: m / z = 704 [(M + 1) ^&lt; ^{+ &}

Synthetic example  4: Compound 77 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 77-1

Intermediate 36-1 (23.79 g, 0.074 mol) , naphthalene-2,6-diyldiboronic acid (15.97 g, 0.074 mol), Pd (PPh 3) 4 (3.47 g, 0.0030 mol, sigma aldrich), K 2 CO 3 ( 17.41 g, 0.126 mol, sigma aldrich) and 250 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 22.99 g (yield 75%) of Intermediate 77-1. (m / z = 414)

(2) Manufacturing example  2: Synthesis of Intermediate 77-2

Intermediate 77-1 (22.99 g, 0.056 mol) , 2,4,6-trichloro-1,3,5-triazine (10.33 g, 0.056 mol, sigma aldrich), Pd (PPh 3) 4 (2.54 g, 0.0022 mol , Sigma aldrich), K ₂ CO ₃ (13.13 g, 0.095 mol, Sigma aldrich) and 200 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 21.77 g (yield 75%) of Intermediate 77-2. (m / z < / RTI > = 518)

(3) Manufacturing example  3: Synthesis of Intermediate 77-3

Intermediate 77-2 (21.77 g, 0.042 mol) , biphenyl-4-ylboronic acid (8.32 g, 0.042 mol, sigma aldrich), Pd (PPh 3) 4 (1.96 g, 0.0017 mol, sigma aldrich), K 2 CO 3 (9.81 g, 0.071 mol, Sigma aldrich) and 150 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and column-purified (n-hexane: MC) to obtain 20.04 g (yield 75%) of Intermediate 77-3. (m / z = 636)

(4) Manufacturing example  4: Synthesis of Compound 77

Intermediate 4-4 (20.04 g, 0.032 mol) , phenanthren-9-ylboronic acid (7.11 g, 0.032 mol, sigma aldrich), Pd (PPh 3) 4 (1.50 g, 0.0013 mol, sigma aldrich), K 2 CO 3 (7.46 g, 0.054 mol, Sigma aldrich) and 100 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 19.91 g (yield 80%) of Compound 77.

8.12 (d, 2H), 7.93-7.73 (m, 14H), 7.58 (d, 2H), 8.09 ~ 7.38 (m, 13H), 7.25 (d, 2H)

LC / MS: m / z = 778 [(M + 1) ^&lt; ^{+ &}

Synthetic example  5: Compound 80 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 80-1

Intermediate 36-1 (23.79 g, 0.074 mol) , anthracene-9,10-diyldiboronic acid (19.67 g, 0.074 mol, yurui), Pd (PPh 3) 4 (3.47 g, 0.0030 mol, sigma aldrich), K 2 CO ₃ (17.41 g, 0.126 mol, Sigma aldrich) and 250 mL of THF were added and reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 25.77 g (yield 75%) of Intermediate 80-1. (m / z = 464)

(2) Manufacturing example  2: Synthesis of intermediate 80-2

Intermediate 80-1 (25.77 g, 0.056 mol) , 2,4,6-trichloro-1,3,5-triazine (10.33 g, 0.056 mol, sigma aldrich), Pd (PPh 3) 4 (2.54 g, 0.0022 mol , Sigma aldrich), K ₂ CO ₃ (13.13 g, 0.095 mol, Sigma aldrich) and 200 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and column-purified (n-hexane: MC) to obtain 23.87 g (yield 75%) of Intermediate 80-2. (m / z = 568)

(3) Manufacturing example  3: Synthesis of Intermediate 80-3

Intermediate 80-2 (23.87 g, 0.042 mol) , biphenyl-4-ylboronic acid (8.32 g, 0.042 mol, sigma aldrich), Pd (PPh 3) 4 (1.96 g, 0.0017 mol, sigma aldrich), K 2 CO 3 (9.81 g, 0.071 mol, Sigma aldrich) and 150 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 21.62 g (yield 75%) of Intermediate 80-3. (m / z = 686)

(4) Manufacturing example  4: Synthesis of Compound 80

Intermediate 5-4 (21.62 g, 0.032 mol) , phenylboronic acid (3.90 g, 0.032 mol, sigma aldrich), Pd (PPh 3) 4 (1.50 g, 0.0013 mol, sigma aldrich), K 2 CO 3 (7.46 g, 0.054 mol, Sigma aldrich) and 100 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 18.64 g (yield 80%) of Compound 80.

2H), 7.91-7.81 (m, 10H), 7.52-7.38 (m, 19H), 7.25 (d, 2H)

LC / MS: m / z = 728 [(M + 1) ^&lt; ^{+ &}

Synthetic example  6: Synthesis of compound 91

(One) Manufacturing example  1: Synthesis of intermediate 91-1

Intermediate 80-2 (23.87 g, 0.042 mol) , biphenyl-2-ylboronic acid (8.32 g, 0.042 mol, sigma aldrich), Pd (PPh 3) 4 (1.96 g, 0.0017 mol, sigma aldrich), K 2 CO 3 (9.81 g, 0.071 mol, Sigma aldrich) and 150 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 21.62 g (yield 75%) of Intermediate 91-1. (m / z = 686)

(2) Manufacturing example  2: Synthesis of Compound 91

Intermediate 91-1 (21.62 g, 0.032 mol) , 9,9-dimethyl-9H-fluoren-1-ylboronic acid (7.62 g, 0.032 mol, Yurui), Pd (PPh 3) 4 (1.50 g, 0.0013 mol, sigma aldrich), K ₂ CO ₃ (7.46 g, 0.054 mol, Sigma aldrich) and 100 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 21.61 g (yield 80%) of Compound 91.

1H NMR (200MHz, CDCl3):? Ppm, 7.91-7.79 (m, 14H), 7.55-7.38 (m, 20H), 7.28

LC / MS: m / z = 845 [(M + 1) ^&lt; ^{+ &}

Synthetic example  7: Synthesis of Compound 121

(One) Manufacturing example  1: Synthesis of intermediate 121-1

Add 350 mL of benzene and add 30 mL of acetonitrile (20.57 g, 0.501 mol, Sigma aldrich), potassium t-butoxide (65.64 g, 0.585 mol, Sigma aldrich) Lt; / RTI &gt; for 12 hours. After completion of the reaction, ether and 2% NaHCO ₃ were added thereto. The layers were separated and column-purified (n-hexane: EA) to obtain 18.56 g (yield: 50%) of Intermediate 121-1. (m / z = 222)

(2) Manufacturing example  2: Synthesis of intermediate 121-2

150 mL of POCl ₃ was added to a solution of Intermediate 121-1 (18.56 g, 0.084 mol), N, N, 9,9-tetramethyl-9H-fluorene-1-carboxamide (24.41 g, 0.092 mol, Yurui) And reacted with stirring. After completion of the reaction, the reaction mixture was cooled, and ammonium hydroxide was added thereto to neutralize the pH. After layer separation into H ₂ O: CHCl ₃ , column purification (n-Hexane: MC) was performed to obtain 23.13 g (yield: 60%) of Intermediate 121-2. (m / z = 458)

(3) Manufacturing example  3: Synthesis of intermediate 121-3

Intermediate 121-2 (23.13 g, 0.050 mol) , 1,4-phenylenediboronic acid (8.29 g, 0.050 mol, sigma aldrich), Pd (PPh 3) 4 (2.31 g, 0.002 mol, sigma aldrich), K 2 CO 3 (11.74 g, 0.085 mol, sigma aldrich) and 200 mL of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 20.42 g (yield 75%) of Intermediate 121-3. (m / z = 544)

(4) Manufacturing example  4: Synthesis of intermediate 121-4

Intermediate 121-3 (20.42 g, 0.038 mol) , 4,6-dibromodibenzo [b, d] furan (12.39 g, 0.038 mol, Yurui), Pd (PPh 3) 4 (1.73 g, 0.0015 mol, sigma aldrich), K ₂ CO ₃ (8.98 g, 0.065 mol, sigma aldrich) and 150 mL of THF were added and reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 21.25 g (yield 75%) of Intermediate 121-4. (m / z = 745)

(5) Manufacturing example  5: Synthesis of Compound 121

Intermediate 121-4 (21.25 g, 0.029 mol) , phenylboronic acid (3.54g, 0.029mol, sigma aldrich), Pd (PPh 3) 4 (1.39g, 0.0012mol, sigma aldrich), K 2 CO 3 (6.77g, 0.049 mol, Sigma aldrich) and 100 ml of THF were added, and the mixture was reacted at 65 DEG C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 17.24 g (yield 80%) of Compound 121.

(M, 10H), 7.55-7.38 (m, 16H), 7.28-7.25 (m, 2H), 7.30 3H), 1.72 (s, 6H)

LC / MS: m / z = 743 [(M + 1) ^&lt; ^{+ &}

Device Embodiments 1 through 12

A blue light emitting organic electroluminescent device having the following device structure was manufactured by employing the compound represented by Formula (I) according to the present invention as a compound of the first electron transporting layer, and the luminescent characteristics including the luminous efficiency were measured.

(20 nm) / first electron transport layer (15 nm) / second electron transport layer (201: Liq 15 nm) / LiF (20 nm) / ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer 1 nm) / Al (100 nm)

In order to form a hole injection layer on the ITO transparent electrode, the hole injection layer was formed by vacuum thermal deposition at a thickness of 5 nm using the following [HAT_CN], and then the hole transport layer was formed by using? -NPB, , The first electron transport layer was formed using the [BH1] as a host compound and the [BD1] as a dopant compound to form a layer having a thickness of about 20 nm. , 77, 80, 91, 109, 121, 135, 163, and 187, respectively. Further, a second electron transport layer (doped with Liq 50% of compound [201] below) was deposited to a thickness of 20 nm, LiF 1 nm and aluminum of 100 nm by vapor deposition to produce an organic electroluminescent device.

Device Comparative Example 1

The organic electroluminescent device for Device Comparison Example 1 was fabricated in the same manner except that the first electron transporting layer was not used in the device structure of Example 1 above.

EXPERIMENTAL EXAMPLE 1: Luminescent characteristics of element embodiments 1 to 12

The voltage, current and luminous efficiency of the organic EL device were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research). The current density was 10 mA / Is defined as " driving voltage " The results are shown in Table 1 below.

Example The first electron transport layer V cd / A QE (%) CIEx CIEy One Formula 1 4.11 8.32 6.74 0.141 0.154 2 Formula 12 4.30 8.22 6.70 0.143 0.154 3 Formula 36 4.25 8.18 6.66 0.145 0.155 4 Formula 51 4.22 8.20 6.75 0.145 0.154 5 77 4.30 8.12 6.62 0.144 0.154 6 80 4.41 8.24 6.68 0.145 0.155 7 Formula 91 4.31 8.43 6.81 0.145 0.155 8 (109) 4.35 8.32 6.60 0.144 0.156 9 Formula 121 4.25 8.31 6.75 0.146 0.154 10 (135) 4.29 8.26 6.70 0.145 0.155 11 163 4.20 8.30 6.60 0.144 0.155 12 187 4.39 8.15 6.65 0.145 0.156 Comparative Example 1 not used 4.24 5.2 4.6 0.147 0.156

It can be seen from the results shown in Table 1 that when the electron transport layer 1 according to the present invention is applied to a compound device, the luminescent properties such as luminous efficiency and quantum efficiency are remarkably superior to those of the conventional device (comparative example) .

[HAT_CN] [? -NPB] [BH1] [BD1] [201]

Claims (6)

An organic light-emitting compound represented by the following formula (I):
(I)

In the above formula (I)
X ₁ is any one selected from the group consisting of S, O, CR ₁ R ₂ and SiR ₃ R ₄ ; X ₂ to X ₄ are the same or different from each other and each independently CR ₅ or N;
L ₁ to L ₃ are each independently a direct bond or a substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group,
Ar ₁ to Ar ₂ are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted C3- A substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl, and a substituted or unsubstituted C 3 -C 30 hetero An aryl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazole group,
Wherein R ₁ to R ₅ are the same or different and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted 3-carbon group And R &_lt; ₅ &_gt; may form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle by being connected to each other or adjacent substituents,
The substituted or unsubstituted heterocyclic group is substituted with one or two or more substituents selected from the group consisting of hydrogen, a halogen group, a nitro group, a hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group and a heterocyclic group, Quot; means that the above substituents are substituted with a connected substituent, or have no substituent. The method according to claim 1,
The organic luminescent compound according to claim 1, wherein the compound represented by Formula (I) is selected from the following [compounds 1] to [193]:

1. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises at least one organic light emitting compound represented by Formula (I) according to Claim 1. The method of claim 3,
Wherein the organic material layer includes at least one of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer and a light emitting layer,
Wherein at least one of the layers comprises an organic light emitting compound represented by the formula (I). 5. The method of claim 4,
Wherein the electron transporting layer comprises an organic light emitting compound represented by the above formula (I). 5. The method of claim 4,
Wherein the electron transporting layer comprises a first electron transporting layer and a second electron transporting layer, and the first electron transporting layer comprises an organic light emitting compound represented by the formula (I).

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