KR101996649B1 - Pyrene derivative compounds and organic light-emitting diode including the same - Google Patents

Abstract

[화학식 4] [화학식 5]

The present invention relates to a novel compound and an organic electroluminescent device comprising the same as a light emitting material, and more particularly to a novel compound represented by the following formulas (1) to (5) and an organic electroluminescent device including the novel compound , And the organic electroluminescent device comprising the light-emitting compounds of the following formulas (1) to (5) according to the present invention has an excellent effect on light emission characteristics such as driving voltage and current efficiency.
[Formula 3] < EMI ID =

[Chemical Formula 4]

Description

[0001] The present invention relates to a pyrene derivative compound and an organic electroluminescent device including the same,

The present invention relates to a pyrene derivative compound and an organic electroluminescent device comprising the same as a light emitting material. More particularly, the present invention relates to a pyrene derivative compound having excellent emission characteristics such as a driving voltage and a current efficiency, Device.

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. On the other hand, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon and has a wide viewing angle and can be made thinner and thinner than a liquid crystal display, And in recent years, application to a full-color display or illumination is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic electroluminescent device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host-dopant system can be used as a light-emitting material in order to increase the light-emitting efficiency through the light-emitting layer.

When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the light of the desired wavelength can be obtained according to the type of the dopant used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

Accordingly, a first technical object of the present invention is to provide a pyrene derivative compound having a low driving voltage and a high luminous efficiency.

A second object of the present invention is to provide an organic electroluminescent device comprising the pyrene derivative compound.

In order to accomplish the first technical object, the present invention provides a pyrene derivative compound represented by the following formulas (1) to (5).

[Formula 3] < EMI ID =

[Chemical Formula 4]

In the above Chemical Formulas 1 to 5,

Ar ₁ to Ar ₆ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms , A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted 5 A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S, a substituted or unsubstituted hetero atom, a substituted Or a group selected from the group consisting of an unsubstituted silicon group, a substituted or unsubstituted boron group, a substituted or unsubstituted silane group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxyl group, a nitro group, a halogen group, And may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with adjacent groups.

Provided that at least three or more of Ar ₁ to Ar ₆ have the structure represented by the following structural formula 1.

[Structural formula 1]

In the above formula 1,

And n and m are each independently an integer of 0 or 1 (provided that n + m > 1)

L is a divalent linking group which is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, A substituted or unsubstituted arylene group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms, a monovalent substituent when n or m is 0,

Wherein B represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted 5 to 30 carbon atoms A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, , A substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, a substituted or unsubstituted silicon group, a substituted or unsubstituted boron group, a substituted or unsubstituted silane group, A condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero ring selected from the group consisting of a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxyl group, a nitro group, a halogen group, an amide group and an ester group, have.

According to an embodiment of the present invention, B in the structural formula 1 is -NR ₁ R ₂ , R ₁ and R ₂ are each a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted Or an unsubstituted or substituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S, or an ester group, and an aliphatic, aromatic , Aliphatic heteroaromatic, or aromatic heteroaromatic rings.

According to another aspect of the present invention,

An organic electroluminescent device comprising an anode, a cathode, and a pyrene derivative compound interposed between the anode and the cathode and represented by the following Chemical Formulas 1 to 5:

According to the present invention, the pyrene derivative compounds represented by the formulas (1) to (5) have stable and excellent luminescent characteristics as compared with the existing materials, and thus the organic electroluminescent device including the same can be operated at low voltage, .

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.

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

The present invention relates to a pyrene derivative compound contained in a light emitting layer of an organic electroluminescent device, which is a compound represented by the following formulas (1) to (5) More specifically, it is as follows.

[Formula 3] < EMI ID =

[Chemical Formula 4]

In the above Chemical Formulas 1 to 5,

Ar ₁ to Ar ₆ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, A substituted or unsubstituted silane group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxyl group, a nitro group, a halogen group, an amide group and an ester group, , To form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with adjacent groups.

Provided that at least three or more of Ar ₁ to Ar ₆ have the structure represented by the following structural formula 1.

[Structural formula 1]

In the above formula 1,

n and m are each independently an integer of 0 or 1 (provided that n + m > 1)

L is a divalent linking group which is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, A substituted or unsubstituted arylene group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms, a monovalent substituent when n or m is 0,

B represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 30 carbon atoms A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, a substituted or unsubstituted silicon group, a substituted or unsubstituted boron group, a substituted or unsubstituted silane group, A condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with an adjacent group selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, .

B in the above formula 1 is -NR ₁ R ₂ , R ₁ and R ₂ are each a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 50 carbon atoms An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, an ester group, and a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero, Can be formed.

In the present invention, the term "substituted or unsubstituted" means a group selected from the group consisting of a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group, an alkoxy group, an alkylamino group, an arylamino group, a heteroarylamino group, an alkylsilyl group, Substituted or unsubstituted with at least one substituent selected from the group consisting of an oxygen atom, an aryl group, a heteroaryl group, germanium, phosphorus, boron, hydrogen and deuterium.

Further, although the range of the present invention is not limited by the more specific examples of the pyrene derivative compound according to the above formula (1), more specifically, the compounds represented by the following formulas (1) to (5) May be any one selected from the group consisting of formulas (6) to (97).

[Chemical Formula 7] < EMI ID =

[Chemical Formula 10] < EMI ID =

[Chemical Formula 12]

[Chemical Formula 14]

[Chemical Formula 16]

[Chemical Formula 19] [Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 25]

[Chemical Formula 27]

[Chemical Formula 32]

[Chemical Formula 33]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 67] [Chemical Formula 68] [Chemical Formula 69]

[Chemical Formula 71] [Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 75] [Chemical Formula 76] [Chemical Formula 77]

[Formula 79] [Formula 80] [Formula 81]

[Chemical Formula 82]

[Chemical Formula 88] [Chemical Formula 88] [Chemical Formula 89]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

Also, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and a pyrene derivative compound interposed between the anode and the cathode, and represented by the above Chemical Formulas 1 to 5.

In this case, the layer containing the novel compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer And at least one layer selected from the group consisting of

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM, and the light emitting layer may further include various phosphorescent host materials.

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A hole injection layer (HIL) may be additionally formed on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenyl amino) triphenylamine) can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, .

The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1. Synthesis of intermediate

(1) Synthesis of 2,7-diiodo-3,8-diphenyl-pyrene

(1-1) Synthesis of 2-bromobiphenylacetylene

To a solution of 2-bromo-iodo-benzene (10 g, 35 mmol), Pd (PPh3) 4 (0.8 g, 0.5 mmol) and CuI (0.54 g, 1 mmol) in 50 mL of triethylamine was stirred at room temperature (Reaction proceeded in nitrogen atmosphere) and phenylacetylene (3.6 mL, 35 mmol) was slowly added.

After stirring for about 1 hour at room temperature, 300 mL of hexane was added to terminate the reaction. The whole solution was passed through silica gel to separate the product, and the column was further drained with 500 mL of hexane. The solvent was removed to give a white product (yield: 98%).

MS (MALDI-TOF): m / z 257 [M] ^&lt; ^{+ &}

(1-2) Synthesis of 2-biphenylacetylenevoronic acid

2-Bromobiphenylacetylene (10 g, 55 mmol) was dissolved in 100 mL of THF. The n-BuLi (50 mL) was added slowly while cooling to -78 ° C. After the addition, trimethylborate (6.57 g, 63 mmol) was added at -78 ° C for about 1 hour. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 2 hours, and 2N HCl was added to adjust the acidity. After the extraction with EA, the solvent was removed, and the solution was diluted with hexane and stirred at -78 ° C to solidify to obtain a white solid. (70% yield)

MS (MALDI-TOF): m / z 257 [M] ^&lt; ^{+ &}

(1-3) Synthesis of 2,2'-diphenylethynylbiphenyl

(9.5 g, 43 mmol), K2CO3 (10.75 g, 78 mmol) and Pd (PPh3) 4 (0.9 g, 1 mmol) were added to a solution of 2-bromobiphenylacetylene (10 g, 55 mmol) Was added to a mixed solution of 100 mL of toluene, 100 mL of THF, and 50 mL of H2O and refluxed. After the reaction was completed, the organic solvent was removed by layer separation, and the product was separated by column separation (MC: Hx = 1: 9) (yield 70%).

MS (MALDI-TOF): m / z 254 [M] ^&lt; ^{+ &}

(1-4) 2,7-diiodo-3,8-diphenyl-pyrene

2,2'-diphenylethynylbiphenyl (10 g, 28 mmol) was dissolved in 100 mL of MC. 68 mL of ICl (1M in MC) was slowly added at room temperature. After stirring at room temperature for 1 hour, iodine was removed with saturated Na2S2O3 and extracted with EA. The product was isolated by column (MC: Hx = 1: 9) (yield 60%).

MS (MALDI-TOF): m / z 606 [M] ^&lt; ^{+ &}

(2) Synthesis of 5,10-dibromo-2,7-diphenyl-pyrene

(2-1) Synthesis of 4,4'-dibromo-2,2'-dinitro-biphenyl.

250 g (0.890 mol) of 2,5-dibromonitrobenzene, 135.74 g (2.136 mol) of copper powder and 1 L of DMF were placed. The temperature of the reactor was raised to 125 캜 and stirred for 3 hours. When the reaction was completed, the temperature was lowered to room temperature, 500 mL of toluene was added, and the mixture was stirred. The insoluble inorganic salts were removed by celite filtration and the filtrate was dried. To the dried filtrate, 2 L of methanol was added and stirred vigorously. The resulting crystals were filtered and dissolved again in 500 mL of toluene. The remaining inorganic salts were removed by celite filtering, and the filtrate was dried. MeOH was added thereto and stirred vigorously to obtain 139 g (77.7%) of 4,4'-dibromo-2,2'-dinitro- .

MS (MALDI-TOF): m / z 402 [M] ^&lt; ^{+ &}

(2-2) Synthesis of 4,4'-dibromo-2,2'-diaminobiphenyl

139.7 g (0.347 mol) of 4,4'-dibromo-2,2'-dinitro-biphenyl was added and 2 L of ethanol was added. Then 1 L of 12 M HCl was added and stirred. The temperature of the reactor was lowered to 0 ° C and 165 g (1.39 mol) of Tin powder was added slowly over 20 minutes. The temperature of the reactor was raised to 100 ° C and refluxed for 3 hours. When the reaction was completed, the temperature of the reactor was lowered to 0 ° C. and 12 M 1 L of sodium hydroxide aqueous solution was slowly added to make the reaction solution basic. Ethylacetate was added to extract the organic layer, and the organic layer was dried and concentrated. (87.7 g, 73.8%) of 4,4'-dibromo-2,2'-diaminobiphenyl was obtained by separating by column chromatography using hexane and methylene chloride as eluent.

MS (MALDI-TOF): m / z 342 [M] ^&lt; ^{+ &}

(2-3) Synthesis of 4,4'-dibromo-2,2'-diiodobiphenyl

87.7 g (0.256 mol) of 4,4'-dibromo-2,2'-diaminobiphenyl, 380 mL of 12 M HCl, and 380 mL of water. The temperature of the reactor was lowered to 0 ° C. Sodium nitrite (44.2 g, 0.641 mol) was dissolved in 220 mL of water and slowly added dropwise to the reactor. When the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour. Potassium iodide was dissolved in 850 mL of water and slowly added dropwise. When the dropwise addition was completed, the solution was stirred at room temperature for 1 hour. The temperature of the reactor was raised to 60 DEG C and stirred for 3 hours. When the reaction was complete, the mixture was cooled to room temperature and extracted with Ethylacetate to separate the organic layer. The separated organic layer was dried over anhydrous, dried and then subjected to column chromatography using hexane as a developing solvent to obtain 42.1 g (29.1%) of 4,4'-dibromo-2,2'-diiodobiphenyl.

MS (MALDI-TOF): m / z 563 [M] ^&lt; ^{+ &}

(2-4) Synthesis of 4,4'-dibromo-2,2'-diphenylethynylbiphenyl

(0.036 mol) of 4,4'-dibromo-2,2'-diiodobiphenyl and 0.7 g (0.0035 mol) of copper iodide and 1.6 g (0.0014 mol) of Pd (PPh3) 4 in a 500 mL round- mol) was dissolved in 200 mL of triethyl amine. 9.3 g (0.085 mol) of phenylacetylene was slowly added dropwise to the reactor and stirred for 1 hour. After the reaction was completed, it was dissolved in MC and filtered using Celite and Silica. The filtrate was dried, and 13.5 g (74.3%) of 4,4'-dibromo-2,2'-diphenylethynylbiphenyl obtained by column chromatography using hexane as eluent was obtained.

MS (MALDI-TOF): m / z 512 [M] ⁺

(2-5) Synthesis of 5,10-dibromo-2,7-diphenyl-pyrene

A 250 mL reactor was charged with 12.3 g (0.024 mol) of 4,4'-dibromo-2,2'-diphenylethynylbiphenyl in a nitrogen stream and dissolved in 120 mL of dichloroethane. Iron (III) trifluoro-methanesulfonate (1.2 g, 0.002 mol) was added and refluxed for 12 hours. After completion of the reaction, the mixture was hot-filtered. The filtrate was dried and EA slurried. The resulting solid was filtered and recrystallized to obtain 2.0 g (16.3%) of 5,10-dibromo-2,7-diphenyl-pyrene.

MS (MALDI-TOF): m / z 512 [M] ⁺

Synthesis Example 2. Synthesis of [Formula 14]

Diphenylamine (3 g, 18 mmol), t-BuONa (3.49 g, 36 mmol), Pd (OAc) 2 (0.15 g, , 0.32 mmol) (t-Bu) 3P (0.53 mL, 1.48 mmol) was added to 50 mL of O-xylene and refluxed for 12 hours or more. After the reaction was completed, the reaction mixture was cooled to room temperature, the solvent was removed, and the product was isolated by column separation (MC: Hx = 1: 7) (yield 80%).

MS (MALDI-TOF): m / z 618 [M] ^&lt; ^{+ &}

Synthesis Example 3. Synthesis of [Formula 41]

The synthesis was carried out in the same manner as in Synthesis Example 2, except that 4,4'-di-tert-butylphenylamine was used instead of diphenylamine.

MS (MALDI-TOF): m / z 913 [M] ^&lt; ^{+ &}

Synthesis Example 4. Synthesis of [Formula 50]

The synthesis was carried out in the same manner as in Synthesis Example 2, except that 4-phenyldiphenylamine was used instead of diphenyl amine.

MS (MALDI-TOF): m / z 841 [M] ^&lt; ^{+ &}

Synthesis Example 5. Synthesis of [Formula 35]

(10 g, 17.2 mmol), Phenyl boronic acid (5.2 g, 43 mmol), K2CO3 (10.75 g, 78 mmol), Pd (PPh3) 4 (0.9 g, 1 mmol) was added to a mixed solution of 100 mL of toluene, 100 mL of THF and 50 mL of H 2 O and refluxed. After the reaction was completed, the organic solvent was removed by layer separation, and the product was separated by column separation (MC: Hx = 1: 9) (yield 70%).

MS (MALDI-TOF): m / z 506 [M] ^&lt; ⁺ & gt ^;

Synthesis Example 6. Synthesis of [Formula 36]

Was synthesized in the same manner as in Synthesis Example 5 and synthesized by using 3-pyridyl boronic acid instead of Phenyl boronic acid.

MS (MALDI-TOF): m / z 508 [M] ^&lt; ⁺ & gt ^;

Synthesis Example 7. Synthesis of [Formula 61]

The intermediate was changed to 5,10-Dibromo-2,7-diphenyl-Pyrene in the same manner as in Synthesis Example 2, and the amine was synthesized as 4,4'-di-tert-butylphenylamine

MS (MALDI-TOF): m / z 913 [M] ^&lt; ^{+ &}

Synthesis Example 8. Synthesis of [Formula 64]

In the same manner as in Synthesis Example 2, the intermediate was changed to 5,10-Dibromo-2,7-Diphenyl-Pyrene and the amine was synthesized with 4-anilinobenzonitrile.

MS (MALDI-TOF): m / z 738 [M] ^&lt; ^{+ &}

Synthesis Example 9. Synthesis of [Formula 72]

The intermediate was synthesized by replacing boronic acid with 4- (N, N-diphenylamino) -1-phenylboronic acid by replacing 5,10-Dibromo-2,7-Diphenyl-Pyrene.

MS (MALDI-TOF): m / z 841 [M] ^&lt; ^{+ &}

Examples 2 to 9

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the ITO glass was mounted in a vacuum chamber, the base pressure was adjusted to 1 × 10 ^-7 torr, and CuPc (800 Å) and α-NPD (300 Å) were sequentially deposited on the ITO. Alq ₃ (350 ANGSTROM), LiF (5 ANGSTROM) and Al (500 ANGSTROM) were deposited in this order to form an organic electroluminescent device.

Comparative Example

The light emitting layer further contains a pyrene compound represented by the following formula (98) as a guest compound, and the host material is a compound represented by the following formula (99).

[Chemical Formula 98]

Evaluation example

The voltage, current density, luminance, color coordinates, and lifetime of the organic electroluminescent device manufactured according to Examples 2, 3, 4, 7, and 8 and Comparative Example 1 were measured and the results are shown in Table 1 Respectively. T97 means the time required for the luminance to be reduced to 97% of the initial luminance.

Voltage Current density (mA / cm 2) Brightness (Cd / m2) CIEx CIEy T97 Example 2 4.02 10 787.7 0.14 0.14 74 Example 3 3.78 10 840.3 0.13 0.12 33 Example 4 3.92 10 513.8 0.13 0.12 118 Example 7 4.09 10 740 0.13 0.12 70 Example 8 4.16 10 810 0.13 0.13 48 Comparative Example 1 5.1 10 560 0.14 0.17 20

As shown in Table 1, the organic electroluminescent device including the organic electroluminescent compound according to the present invention has a low driving voltage and is excellent in light emission characteristics such as brightness and lifetime and can be utilized in various display devices.

10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

Claims (8)

A pyrene derivative compound represented by the following Chemical Formulas 1 to 5:
[Formula 3] &lt; EMI ID =

[Chemical Formula 4]

In the above Chemical Formulas 1 to 5,
Ar ₁ to Ar ₆ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, An aryl group having 5 to 50 carbon atoms, and a heteroaryl group having 3 to 50 carbon atoms having a substituted or unsubstituted heteroatom, O, N or S, with the proviso that Ar ₃ and Ar _{6 in the} formula [4] ], Ar ₂ and Ar ₄ are each a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms,
At least three of Ar ₁ to Ar ₆ are represented by the following structural formula 1,
[Structural formula 1]

In the above formula 1,
n and m are each independently an integer of 0 or 1 (provided that n + m &gt; = 1)
L is a divalent linking group selected from a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms,
Provided that when m is 0, L is a monovalent substituent, and when n is 0, L means a single bond,
B represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroatom such as O, N or S, with the proviso that Ar ₃ and Ar _{6 in the} formula (4) and Ar ₂ and Ar ₄ in the formula (5) each represent a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, An arylamine group having 5 to 30 carbon atoms is excluded). The method according to claim 1,
B in the above structural formula 1 is -NR ₁ R ₂ , R ₁ and R ₂ are a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, or a substituted or unsubstituted heteroatom such as O, N or S And R &lt; 3 &gt; is a heteroaryl group having 3 to 50 carbon atoms. The method according to claim 1,
[Formula 6] to [Formula 50], [Formula 53] to Formula [57], [Formula 60] to Formula [65], [Formula 67] Wherein the pyrene derivative compound is any one selected from the group consisting of the following formulas (70) to (85), (87) to (95)
[Chemical Formula 7] &lt; EMI ID =

[Chemical Formula 10] &lt; EMI ID =

[Chemical Formula 12]

[Chemical Formula 14]

[Chemical Formula 16]

[Chemical Formula 19] [Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 25]

[Chemical Formula 27]

[Chemical Formula 32]

[Chemical Formula 33]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 60]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 67]

[Chemical Formula 71] [Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 75] [Chemical Formula 76] [Chemical Formula 77]

[Formula 79] [Formula 80] [Formula 81]

[Chemical Formula 82]

[Chemical Formula 88] [Chemical Formula 88]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 95]

Anode;
Cathode; And
The organic electroluminescent device according to any one of claims 1 to 3, interposed between the anode and the cathode. 5. The method of claim 4,
Wherein the compound is contained in the light emitting layer between the anode and the cathode. 6. The method of claim 5,
Wherein at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. The method according to claim 6,
Wherein at least one layer selected from the group consisting of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecular deposition method or a solution process. 5. The method of claim 4,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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