KR102052332B1 - Phenanthroline compound and organic light emitting element comprising the same - Google Patents

Abstract

The present invention relates to a phenanthroline compound and an organic electroluminescent device exhibiting excellent efficiency characteristics by including the phenanthroline compound in one or more organic layers. An organic light emitting device according to the present invention has excellent electrochemical and thermal stability, excellent lifespan characteristics, and has high luminous efficiency even at a low driving voltage.

Description

PHENANTHROLINE COMPOUND AND ORGANIC LIGHT EMITTING ELEMENT COMPRISING THE SAME

The present invention relates to a phenanthroline compound and an organic light emitting device comprising the same.

Organic light emitting diodes (OLEDs) are attracting attention as the demand for flat panel displays increases. In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.

Such an organic light emitting device converts electrical energy into light by applying a current to an organic light emitting material, and has a structure in which a functional organic material layer is inserted between an anode and a cathode. In this case, the organic material layer is often composed of a multilayer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. Can be.

When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer in the anode and electrons in the cathode, and the injected holes and the electrons meet and recombine by recombination. High energy excitons are formed. At this time, the excitons formed are moved to the ground state, and light having a specific wavelength is generated.

Recently, it has been known that not only fluorescent light emitting materials but also phosphorescent light emitting materials can be used as light emitting materials of organic light emitting devices. Such phosphorescent light emitting is carried out from the ground state to the excited state after the electron transition, and the intersystem crossing (intersystem crossing) It is composed of a mechanism in which the singlet excitons are non-luminescent transition into triplet excitons, and then the triplet excitons emit light as they transition to the ground state.

Patent Document 1: Korean Patent Publication No. 10-2017-0052764

An object of the present invention is to provide a phenanthroline compound of a novel structure and an organic light emitting device comprising the same.

Another object of the present invention to provide a compound for an organic light emitting device having properties such as high efficiency and long life.

The present invention also provides an image display device including the compound for an organic light emitting device.

An object of the present invention can be achieved by the phenanthroline compound represented by the following formula (1).

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a single bond, a substituted or unsubstituted arylene group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and a combination thereof Ar ₃ and Ar ₄ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aryl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and a combination thereof L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 3 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms.

Ar ₁ and Ar ₂ are each independently a single bond, substituted or unsubstituted phenylene, alkylphenylene, halophenylene, cyanophenylene, naphthylene, alkylnaphthylene, biphenylene, alkylbiphenylene, Pyridylene, pyrimidylene, quinolinilene, isoquinolinylene, quinoxalinylene, pyrazinylene, quinazolinylene, naphthyridinylene, openylene, furanylene, benzothiophenylene, benzofuranylene, dibenzo Thiophenylene, dibenzofuranylene, fluorenylene, carbazoylene, imidazolylene, triphenylenylene, fluoroantenylene and diacafluorenylene.

At least one of Ar ₃ and Ar ₄ may be a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms having electronic properties.

Substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms having the above electronic properties is substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted It may be selected from the group consisting of a quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, and a substituted or unsubstituted isoquinolinyl group.

The substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms having the above electronic properties may be selected from the group consisting of substituents represented by the following Formulas A-1 to A-5:

L ₁ and L ₂ are each independently a single bond, substituted or unsubstituted phenylene, alkylphenylene, halophenylene, cyanophenylene, naphthylene, alkylnaphthylene, biphenylene, alkylbiphenylene, Pyridylene, pyrimidylene, quinolinilene, isoquinolinylene, quinoxalinylene, pyrazinylene, quinazolinylene, naphthyridinylene, openylene, furanylene, benzothiophenylene, benzofuranylene, dibenzo Thiophenylene, dibenzofuranylene, fluorenylene, carbazoylene, imidazolylene, triphenylenylene, fluoroantenylene and diacafluorenylene.

In addition, an object of the present invention comprises a first electrode, a second electrode, and at least one organic layer positioned between the first electrode and the second electrode, wherein at least one of the organic layer is phenanthroline according to the present invention It can be achieved by an organic light emitting device comprising a compound.

The organic material layer may include at least one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, and a layer simultaneously performing hole injection and hole transport.

The organic material layer may include at least one layer selected from the group consisting of a light emitting layer, an electron injection layer, an electron transport layer, and a layer for simultaneously performing electron injection and electron transport.

The organic material layer may include at least one charge generation layer (CGL).

In addition, an object of the present invention can be achieved by an image display device including an organic light emitting device according to the present invention.

According to the present invention there is provided a phenanthroline compound of a novel structure.

The organic light emitting device according to the present invention has excellent electrochemical and thermal stability, excellent life characteristics, and high luminous efficiency even at a low driving voltage.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art to which the present invention pertains. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims.

The size and thickness of each component shown in the drawings are shown for convenience of description, and the present invention is not necessarily limited to the size and thickness of the illustrated configuration.

Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.

The phenanthroline compound according to the present invention is represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

Ar ₁ and Ar ₂ are each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and a combination thereof,

Ar ₃ and Ar ₄ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aryl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and a combination thereof,

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 3 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms.

By using a compound having an appropriate energy level in the organic light emitting device according to the substituent of the compound, the hole transport ability or electron transfer ability is enhanced to have an excellent effect in efficiency and driving voltage, etc., and excellent in electrochemical and thermal stability organic light emitting device Its life characteristics can be improved during operation.

More specifically, in one embodiment of the present invention, a substituted or unsubstituted 3 to 30 aryl group and or a substituted or unsubstituted C 3 to 30 heteroaryl group is a substituted or unsubstituted phenyl group, substituted or unsubstituted Naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenylyl group, substituted or substituted Unsubstituted p-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted or unsubstituted chrysenyl groups, substituted or unsubstituted triphenylenyl groups, substituted or unsubstituted peryleneyl groups, substituted or unsubstituted Indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or substituted Unsubstituted pyrrolyl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted Or an unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted Triazinyl groups, substituted or unsubstituted benzofuranyl groups, substituted or unsubstituted benzothiophenyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted quinolinyl groups, substituted Or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or Unsubstituted quinoxalinyl groups, substituted or unsubstituted naphthyridinyl groups, substituted or unsubstituted benzoxazinyl groups, substituted or unsubstituted benzthiazinyl groups, substituted or unsubstituted acridinyl groups, substituted or unsubstituted Phenazineyl group, substituted or unsubstituted phenothiazineyl group, substituted or unsubstituted phenoxazineyl group, or a combination thereof, but is not limited thereto.

In addition, by adjusting the Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ can be determined the conjugation (conjugation) length of the compound premises, from this it is possible to control the triplet (bandlet) energy bandgap. Through this, it is possible to realize the characteristics of the material required by the organic light emitting device. In addition, triplet energy bandgap can be adjusted by changing the binding position of olso, para, meta. More specifically, by adjusting HOMO and LUMO energy, dipole moment, molecular weight, and the like of the entire compound, the driving voltage in the device may be improved by reducing the energy difference between adjacent layers.

L ₁ , L ₂ , Ar _1, and Ar ₂ are each independently a single bond, a substituted or unsubstituted phenylene, alkylphenylene, halophenylene, cyanophenylene, naphthylene, alkylnaphthylene, biphenylene , Alkylbiphenylene, pyridylene, pyrimidylene, quinolinylene, isoquinolinylene, quinoxalinylene, pyrazinylene, quinazolinylene, naphthyridinylene, openylene, furanylene, benzothiophenylene, It may be selected from the group consisting of benzofuranylene, dibenzothiophenylene, dibenzofuranylene, fluorenylene, carbazoylene, imidazolylene, triphenylenylene, fluoranthylene and diacafluorenylene.

At least one of Ar ₃ and Ar ₄ may be a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms having electronic properties.

More specifically, for example, the substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms having the above electronic properties may be substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, or substituted or unsubstituted tetrazolyl. Groups, substituted or unsubstituted oxadiazolyl groups, substituted or unsubstituted oxatriazolyl groups, substituted or unsubstituted thiazazolyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted benzo Triazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted pyridazinyl group, Substituted or unsubstituted purinyl group, substituted or unsubstituted quinolinyl group, substituted or substituted Unsubstituted isoquinolinyl group, substituted or unsubstituted phthalazinyl group, substituted or unsubstituted naphpyridinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted It may be an acridinyl group, a substituted or unsubstituted phenanthrolinyl group, or a substituted or unsubstituted phenazinyl group. However, it is not limited thereto.

More preferably, the substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms having the above electronic properties is a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, It may be a substituted or unsubstituted quinolinyl group, or a substituted or unsubstituted isoquinolinyl group. In this case, electron mobility may be improved while having an appropriate energy band gap, thereby improving efficiency and lifespan of the device.

Even more preferably, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms having the above electronic properties may be represented by any one of the following Formulas A-1 to A-5. However, it is not limited thereto.

For example, the phenanthroline compound according to the present invention may be a compound shown below.

The phenanthroline compound according to the present invention can be described in more detail through the following structural formula.

[Formula 2]

The phenanthroline compound in Formula 2 is a stable aromatic compound. However, due to the effects of nitrogen atoms at 1 and 10, carbons 2 and 9 are partially positively charged and are deficient in electrons. Carbon atoms at these positions are less stable than other carbon atoms. The phenanthroline compound has a lower reactivity of an electrophilic substitution reaction than an aromatic compound. Therefore, in the substitution reaction of the phenanthroline compound, the bromination reaction is reacted at the 3rd and 8th carbon positions and the nucleophilic substitution reaction is easily reacted at the 2nd and 9th carbons. Therefore, the introduction of an aryl group on the 2nd and 9th carbons and on the 4th and 7th carbons of the phenanthroline compound eliminates the electron deficiency of the phenanthroline compound, increases the stability and enriches the electrons in the nitrogen atom.

[Formula 3]

BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and BPhen (4,7-diphenyl-1,10-phenanthroline) shown in Chemical Formula 3 are compounds based on phenanthroline Furnace is an example of representative compounds used in the electron transport layer in the organic light emitting device. The compound has a structure in which a simple aryl group is introduced at Nos. 4, 7 or 2, 9, 4 and 7 and is symmetric with each other. Compounds studied in the present invention introduced asymmetric substituents at Nos. 2 and 4 instead of symmetrical structures, and particularly, compounds having excellent electron transport and stability by introducing at least one heteroaryl group at Nos. 2 and 4 Was designed.

[Formula 4]

In Formula 4, an electron-rich aromatic compound was introduced at positions 2 or 4 of the phenanthroline core, and in particular, at least one heteroaryl group was introduced to the aromatic compound at positions 2 and 4. This compound can realize excellent performance in current efficiency, external quantum efficiency (EQE), etc. when manufacturing an organic light emitting device.

 By introducing various heteroaryl groups at positions 2 or 4 of the phenanthroline core as described above, the organic light emitting device can be used for various purposes. For example, the hole blocking layer materials used in the manufacture of the organic light emitting device may have an energy level sufficient to block holes passing along the highest occupied molecular orbital (HOMO), and cross the lower unoccupied molecular orbital (LUMO) from the cathode. It is possible to use a compound having an energy level enough to transfer electrons to the light emitting layer. In the n-type charge generation layer (n-CGL), nitrogen of the sp2 hybrid orbital is included, and the nitrogen combines with alkali metal or alkaline earth metal, which is a dopant of the n-type charge generation layer, to form a gap state. Therefore, the transfer of electrons from the p-type charge generation layer (p-CGL) to the n-type charge generation layer (n-CGL) can be facilitated by the gap state. In particular, the core structure of the present compound shows stable properties to the electrons and may contribute to improving the life of the device. Derivatives formed by introducing substituents to be used in the light emitting layer and the electron transport layer material may be manufactured to have an appropriate energy band gap in various arylamine dopants, aryl dopants, metal dopants, and the like.

 In addition, by introducing a variety of substituents in the core structure it is possible to finely control the energy band gap, on the other hand to improve the interfacial properties between the organic material and to vary the use of the material.

 On the other hand, the compounds represented by Formula 1 have a high glass transition temperature (Tg) is excellent in thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention. Referring to FIG. 1, the organic light emitting diode 1 has a tandem structure and includes a first electrode (anode 110), a second electrode (cathode 120), a first light emitter 210, and a second light emitter 220. The third light emitting unit 230 may include a first charge generation layer 240 and a second charge generation layer 250.

The first light emitting unit 210, the second light emitting unit 220, the third light emitting unit 230, the first charge generating layer 240, and the second charge generating layer 250 are organic layers and the first electrode 110. The first charge generation layer 240 is located between the first light emitting part 210 and the second light emitting part 220, and the second charge generation layer 250 is formed between the second electrode 120 and the second electrode 120. The light emitting unit 220 is positioned between the second light emitting unit 220 and the third light emitting unit 230.

The first light emitting unit 210 includes a hole injection layer 211, a first hole transport layer 212, a first light emitting layer 213, and a first electron transport layer 214, and the second light emitting unit 220 is formed of a first light emitting layer 220. The second hole transport layer 221, the second light emitting layer 222 and the second electron transport layer 223, the third light emitting unit 230 is a third hole transport layer 231, the third light emitting layer 232, the third The electron transport layer 233 and the electron injection layer 234.

The first charge generation layer 240 is composed of an n-type charge generation layer 241 and a p-type charge generation layer 242, and the second charge generation layer 250 is an n-type charge generation layer 251 and p-type. The charge generation layer 252. The n-type charge generation layers 241 and 251 may be doped with an alkali metal.

The phenanthroline compound according to the present invention includes a first electron transport layer 214, a second electron transport layer 223, a third electron transport layer 233, an electron injection layer 234, a first charge generating layer 240, and / Alternatively, the second charge generation layer 250 may be included and used, and in particular, may be used in the n-type charge generation layers 241 and 251.

The organic light emitting device 1 described above can be variously modified. Some organic layers may be omitted or added, may not be tandem, or may be tandem with two or more light emitting layers. In addition, the organic light emitting device 1 may include an organic layer including a layer for simultaneously performing electron transport and electron injection. In this case, the phenanthroline compound according to the present invention may be used.

Hereinafter, examples of the phenanthroline compound according to the present invention and examples and comparative examples of the organic light emitting device will be described. However, the preparation examples and examples described below are merely for illustrating or explaining the present invention in detail, and the present invention should not be construed as being limited to the preparation examples and examples described below.

Preparation Example of Compound 1

Synthesis of Intermediate A

289 g (5167 mmol) of potassium hydroxide was dissolved in 1 L of MeOH in a 2 L three-necked flask and cooled to 0 ° C. After nitrogen substitution, 50 g (287.09 mmol) of 8-nitroquinoline was dissolved in 300 ml of THF and added. After stirring at the same temperature for 30 minutes. 39.9 ml (344.51 mmol) of phenylacetonitrile were added thereto. It stirred at 0 degreeC for 3 hours. After the reaction was completed, H ₂ O 2 L was added and precipitated, and washed three times with water. After drying was purified by column chromatography and crystallized with n-Hexane to give 46 g (65%) as intermediate A.

Synthesis of Intermediate B

In a 1 L three-necked flask, 24.7 g (100.3 mmol) of intermediate A and 16.8 g of iron powder were dissolved in 300 ml of acetic acid and stirred under reflux for 3 hours. After the reaction was completed, the mixture was cooled, neutralized with aqueous potassium carbonate solution, extracted with Methylene Chloride, the solvent was removed by distillation under reduced pressure, and purified by column chromatography to obtain Intermediate B 20 g (80.3%).

Synthesis of Intermediate C

20 g (75 mmol) of 2-chlor-4,6-diphenyltriazine and 12.3 g (75 mmol) of 4-acetylphenylboronic acid were added to a 1 L three-neck flask. 41 g (300 mmol) of potassium carbonate and 2.25 g (2.25 mmol) of Pd (PPh ₃ ) ₄ were added, followed by nitrogen replacement in a mixed solution of 200 ml of toluene, 100 ml of H ₂ O and 100 ml of ethanol for 5 hours. Stirring to reflux. After completion of the reaction was extracted with Methylene Chloride and the organic layer was dried over MgSO ₄ and purified by column chromatography to crystallize in MeOH to give 19 g (72.1%) as intermediate C.

Synthesis of Compound 1

In a 500 ml three necked round bottom flask, 12.4 g (50 mmol) of intermediate B, 17.5 g (50 mmol) of intermediate C, and 200 ml of toluene were added and stirred for 15 minutes. Then, 14.4 g (150 mmol) of methanesulfonic acid was added thereto for 8 hours. It was refluxed. After the reaction was completed, the mixture was cooled and neutralized with aqueous potassium carbonate solution, extracted with Methylene Chloride, and the solvent was removed by distillation under reduced pressure. Then purified by column chromatography and crystallized with MeOH to give 18 g (63.8%) as compound 1.

Compound 1 was subjected to NMR measurement using Avance-500 (Bruker), and GC-MS measurement was performed using JMS-700, 6890 Series.

¹ H-NMR: (CDCl ₃ , ppm); 9.37 (s, 1H), 8.95-8.93 (d, 2H), 8.82-8.80 (q, 4H), 8.64-8.62 (d, 2H), 8.33-8.31 (d, 1H), 8.18 (s, 1H), 7.97-7.95 (d, 1H), 7.76-7.71 (m, 2H), 7.65-7.56 (m, 11H)

MS: m / e = 563.2

Preparation Example of Compound 5

Synthesis of Intermediate D

Into a 500 ml three-necked round bottom flask, 28.2 g (113.58 mmol) of intermediate B, 22.6 g (113.58 mmol) of 4-bromoacetophenone, and 300 ml of toluene were stirred for 15 minutes, followed by 32.74 g (340.74 mmol) of methanesulfonic acid. It was refluxed for 8 hours. After the reaction was completed, the mixture was cooled, neutralized with aqueous potassium carbonate solution, extracted with Methylene Chloride, and the solvent was removed by distillation under reduced pressure. Purification by column chromatography and crystallization with MeOH gave 35 g (74.9%) as intermediate D.

Synthesis of Intermediate E

38.8 g (100 mmol) of 2- (4-bromophenyl) -4,6-diphenyltriazine, 2.7 g (3 mmol) of Pd ₂ (dba) _{3 in a} 500 ml three-necked round bottom flask, tricyclohexylphosphate 2.21 g (6 mmol) of pins, 55.9 g (220 mmol) of bis (pinacorate) diborane, 39.25 g (400 mmol) of potassium acetate were substituted with nitrogen, and 300 ml of 1,4-dioxane was added to reflux to obtain 4 Stirred for hours. After completion of the reaction, the mixture was extracted with Methylene Chloride, the organic layer was dried over MgSO ₄ and purified by column chromatography and crystallized with n-Hexane to give 38 g (87.3.%) As intermediate E.

Synthesis of Compound 5

10 g (24.31 mmol) of Intermediate D and 10.5 g (24.3 mmol) of Intermediate E were charged into a 500 ml three-neck flask. 13.4 g (97.2 mmol) of potassium carbonate and 0.84 g (0.729 mmol) of Pd (PPh ₃ ) ₄ were added thereto, followed by nitrogen replacement in a mixed solution of 100 ml of toluene, 50 ml of H ₂ O and 50 ml of ethanol, and refluxed for 5 hours. Stirring while stirring. After completion of the reaction, the mixture was extracted with Methylene Chloride, the organic layer was dried over MgSO ₄ and purified by column chromatography to crystallize with MeOH to give 9 g (58%) as a compound 5.

NMR measurement was performed using Avance-500 (Bruker) for Compound 5, and GC-MS measurement was performed using JMS-700, 6890 Series.

¹ H-NMR: (CDCl ₃ , ppm); 9.42-9.41 (d, 1H), 8.88-8.86 (m, 2H), 8.82-8.80 (m, 4H), 8.64-8.62 (d, 2H), 8.38-8,37 (d, 1H), 8.16 (s , 1H), 7.98-7.97 (d, 1H), 7.93-7.90 (m, 4H), 7.77-7.74 (q, 2H), 7.65-7.56 (m, 11H)

MS: m / e = 639.2

Preparation of Compound 7

Synthesis of Intermediate F

38.8 g (100 mmol) of 2- (3-bromophenyl) -4,6-diphenyltriazine, 2.7 g (3 mmol) of Pd ₂ (dba) _{3 in a} 500 ml three-necked round bottom flask, tricyclohexylphosphate 2.21 g (6 mmol) of pins, 55.9 g (220 mmol) of bis (pinacorate) diborane, 39.25 g (400 mmol) of potassium acetate were substituted with nitrogen, and 300 ml of 1,4-dioxane was added to reflux to obtain 4 Stir for hours. After completion of the reaction, the mixture was extracted with Methylene Chloride, the organic layer was dried over MgSO ₄ , purified by column chromatography, and crystallized with n-Hexane to give 35 g (80.4.%) As intermediate F.

Synthesis of Compound 7

10 g (24.31 mmol) of Intermediate D and 10.5 g (24.3 mmol) of Intermediate F were charged into a 500 ml three neck flask. Reflux for 5 hours with nitrogen in a mixture of potassium carbonate and 13.4 g (97.2 mmol) and _{Pd (PPh 3) 4 0.84 g} (0.729 mmol) of 100 ml, H ₂ O 50 ml one input and then toluene, ethanol 50 ml Stirring while stirring. After completion of the reaction was extracted with Methylene Chloride, the organic layer was dried over MgSO ₄ and purified by column chromatography and crystallized with MeOH to give 11 g (71%) as compound 7.

NMR measurements were performed using Compound Avance-500 (Bruker), and GC-MS measurements were performed using JMS-700, 6890 Series.

¹ H-NMR: (CDCl ₃ , ppm); 9.46 (s, 1H), 9.12-9.11 (t, 1H), 8.84-8.79 (m 5H), 8.71-8.70 (d, 2H), 8.43-8.42 (d, 1H), 8.21 (s, 1H), 8.02 -7.95 (m, 4H), 7.80-7.77 (m, 2H), 7,71-7.68 (t, 1H), 7.65-7.57 (m, 11H)

MS: m / e = 639

Preparation Example of Compound 9

Synthesis of Intermediate G

In a 500 ml three necked round bottom flask, 38.7 g (100 mmol) of 4- (4-bromophenyl) -2,6-diphenylpyrimidine, 2.7 g ( ₃ mmol) of Pd ₂ (dba) ₃ , tricyclohexylphosphine 2.21 g (6 mmol), 55.9 g (220 mmol) of bis (pinacorate) diborane, 39.25 g (400 mmol) of potassium acetate were substituted with nitrogen, and 300 ml of 1,4-dioxane was added to reflux for 4 hours. Was stirred. After completion of the reaction, the mixture was extracted with Methylene Chloride, the organic layer was dried over MgSO ₄ , purified by column chromatography, and crystallized with n-Hexane to give 36 g (82.9.%) As an intermediate G.

Synthesis of Compound 9

10 g (24.31 mmol) of Intermediate D and 10.5 g (24.3 mmol) of Intermediate G were charged to a 500 ml three neck flask. 13.4 g (97.2 mmol) of potassium carbonate and 0.84 g (0.729 mmol) of Pd (PPh ₃ ) ₄ were added thereto, followed by nitrogen substitution in a mixed solution of 100 ml of toluene, 50 ml of H ₂ O, and 50 ml of ethanol for 5 hours. Stirring to reflux. After completion of the reaction was extracted with Methylene Chloride, the organic layer was dried with MgSO ₄ and purified by column chromatography to crystallize with MeOH to give 11.6 g (74.7%) as compound 9.

NMR measurement was performed using Compound Avance-500 (Bruker), and GC-MS measurement was performed using JMS-700, 6890 Series.

¹ H-NMR: (CDCl ₃ , ppm); 9.43-9.45 (q, 1H), 9.3-9.33 (d, 1H), 8.73-8.74 (d, 2H), 8.63-8.65 (m, 2H), 8.48-8.50 (d, 2H), 8.44 (s, 1H ), 8.33-8.37 (m, 3H), 8.27 (s, 1H), 8.16-8.22 (q, 2H), 7.89-7.94 (q, 4H), 7.48-7.63 (m, 11H)

MS: m / e = 638

Preparation of Compound 33

Synthesis of Intermediate H

289 g (5167 mmol) of potassium hydroxide was dissolved in 1 L of MeOH in a 2 L three-necked flask and cooled to 0 ° C. After nitrogen substitution, 50 g (287.09 mmol) of 8-nitroquinoline was dissolved in 300 ml of THF and added. After stirring at the same temperature for 30 minutes. 56.26 g (287.09 mmol) of 4-bromophenylacetonitrile was added thereto. It stirred at 0 degreeC for 3 hours. After the reaction was completed, H ₂ O 2 L was added and precipitated, and washed three times with water. After drying, purification by column chromatography and crystallization with n-Hexane to give 45.5 g (48.7%) as intermediate H.

Synthesis of Intermediate I

In a 1 L three-necked flask, 45.5 g (140 mmol) of intermediate H and 23.5 g of iron powder were dissolved in 600 ml of acetic acid and stirred under reflux for 3 hours. After the reaction was completed, the mixture was cooled, neutralized with aqueous potassium carbonate solution, extracted with Methylene Chloride, the solvent was removed by distillation under reduced pressure, and purified by column chromatography to obtain 37.5 g (81.9%) as an intermediate I.

Synthesis of Intermediate J

37.5 g (114.6 mmol) of Intermediate I, 27.6 g (229.2 mmol) of acetophenone, and 65.4 g (346.8 mmol) of methanesulfonic acid were added to a 500 ml three necked round bottom flask, and the mixture was heated and stirred at 110 ° C. for 8 hours. After completion of the reaction, the mixture was cooled and neutralized with aqueous potassium carbonate solution, then extracted with Methylene Chloride, the solvent was removed by distillation under reduced pressure, and purified by column chromatography to obtain 36 g (76.4%) as an intermediate J.

Synthesis of Compound 33

Into a 500 ml three necked flask was charged 10 g (24.31 mmol) of Intermediate J and 10.5 g (24.3 mmol) of Intermediate E. 13.4 g (97.2 mmol) of potassium carbonate and 0.84 g (0.729 mmol) of Pd (PPh ₃ ) ₄ were added thereto, followed by nitrogen substitution in 100 ml of toluene, 50 ml of H ₂ O, and 50 ml of ethanol, followed by reflux for 5 hours. Stirred. After completion of the reaction was extracted with Methylene Chloride, the organic layer was dried over MgSO ₄ and purified by column chromatography to crystallize with MeOH to give 7.5 g (48.3%) as a compound 33.

Compound 33 was subjected to NMR measurements using Avance-500 (Bruker), and GC-MS measurements were performed using JMS-700, 6890 Series.

¹ H-NMR: (CDCl ₃ , ppm); 9.3 (s, 1H), 8.92, 8.94 (d, 2H), 8.82-8.83 (m 4H), 8.4, 8.42 (d, 2H), 8.28, 8.30 (d, 1H), 8.13 (s, 1H), 8.01 , 8.03 (d, 1H), 7.94-7.95 (m, 4H), 7.74-7.78 (m, 3H), 7.67-7.7 (q, 1H), 7.55-7.62 (m, 8H), 7.49-7.51 (m, 1H)

MS: m / e = 639

Preparation of Compound 35

Synthesis of Compound 35

Into a 500 ml three neck flask was charged 10 g (24.31 mmol) of intermediate J and 10.5 g (24.3 mmol) of intermediate F. 13.4 g (97.2 mmol) of potassium carbonate and 0.84 g (0.729 mmol) of Pd (PPh ₃ ) ₄ were added thereto, followed by nitrogen substitution in a mixed solution of 100 ml of toluene, 50 ml of H ₂ O, and 50 ml of ethanol for 5 hours. Stirring to reflux. After completion of the reaction was extracted with Methylene Chloriode, the organic layer was dried over MgSO ₄ and purified by column chromatography and crystallized with MeOH to give 9.5 g (61.3%) as a compound 35.

Compound 35 was subjected to NMR measurement using Avance-500 (Bruker), and GC-MS measurement was performed using JMS-700, 6890 Series.

¹ H-NMR: (CDCl ₃ , ppm); 9.32 (s, 1H), 9.12 (s, 1H), 8.82-8.83 (m 5H), 8.42, 8.44 (d, 2H), 8.30, 8.31 (d, 1H), 8.15 (s, 1H), 8.05, 8.07 (d, 1H), 7.96-7.99 (m, 3H), 7.74-7.79 (m, 4H), 7.69-7.7 (q, 1H), 7.56-7.64 (m, 8H), 7.48-7.51 (m, 1H)

MS: m / e = 639

Preparation of Compound 39

Synthesis of Compound 39

Into a 500 ml three-necked flask was charged 10 g (24.31 mmol) of intermediate J and 10.5 g (24.3 mmol) of intermediate G. 13.4 g (97.2 mmol) of potassium carbonate and 0.84 g (0.729 mmol) of Pd (PPh ₃ ) ₄ were added thereto, followed by nitrogen substitution in a mixed solution of 100 ml of toluene, 50 ml of H ₂ O, and 50 ml of ethanol for 5 hours. Stirring to reflux. After completion of the reaction was extracted with Methylene Chloride, the organic layer was dried over MgSO ₄ and purified by column chromatography and crystallized with MeOH to give 10.3 g (66.3%) as compound 39.

NMR measurements were performed using Avance-500 (Bruker) for Compound 39, and GC-MS measurements were performed using JMS-700, 6890 Series.

¹ H-NMR: (CDCl ₃ , ppm); 9.32 (s, 1H), 8.76-8.78 (m 2H), 8.46-8.47 (m, 4H), 8.33-8.35 (m, 3H), 8.11, 8.13 (d, 2H), 8.02, 8.04 (d, 1H) , 7.92, 7.94 (d, 3H), 7.88-7.89 (m, 1H), 7.75-7.79 (m, 3H), 7.71-7.73 (m, 1H), 7.56-7.58 (m, 7H), 7.46-7.51 ( m, 2H)

MS: m / e = 638

Fabrication of Organic Light Emitting Diode

1. Preparation Example 1

The ITO substrate was patterned so that the light emitting area became 2 mm × 2 mm in size, and then washing was performed with isopropyl alcohol and UV ozone, respectively. Thereafter, the ITO substrate was mounted on the substrate holder of the vacuum deposition apparatus and pressure was applied such that the vacuum degree was 1 × 10 ⁻⁷ torr. Thereafter, plasma treatment was performed for 3 minutes under N ₂ atmosphere.

First, a HAT-CN compound was vacuum deposited to form a 5 nm thick. This compound acts as a hole injection layer. An NPB material was formed to a thickness of 50 nm as a first hole transport layer thereon. Subsequently, the HT-1 material was formed to a thickness of 10 nm as the second hole transport layer.

Thereafter, the GH-1 material was co-deposited at a thickness of 30 nm so that the GD-1 material was doped with a dopant to about 10% by mass to form a green light emitting layer.

An electron transport layer was formed on the light emitting layer with an ET-1 compound having a thickness of 35 nm. Then, LiF material was deposited to form an electron injection layer having a thickness of 1 nm. Thereafter, Al was deposited to a thickness of 100 nm to form a cathode to fabricate an organic EL device.

2. Preparation Example 1

The organic light emitting device was manufactured in the same manner as in the comparative example, except that only the electron transporting material was changed to Compound 1.

3. Preparation Example 2

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transport material with compound 7.

4. Preparation Example 3

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transport material with compound 5.

5. Preparation Example 4

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transport material with compound 9.

6. Preparation Example 5

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transport material with the compound 33.

7. Preparation Example 6

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transporting material with compound 35.

8. Preparation Example 7

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the electron transporting material with compound 39.

The luminescence properties were measured by PR-670, a photoresearch company, by applying a constant current of 10 mA / cm ² to the organic light emitting devices manufactured by Examples 1 to 7 and Comparative Example 1 of the present invention.

Hereinafter, the current density, driving voltage, current efficiency, and external quantum efficiency of the organic light emitting diodes of Examples 1 to 7 and Comparative Example 1 were measured and shown in Table 1 below.

matter Drive current
J (mA / cm ² ) Driving voltage
(Voltage) Current efficiency
(cd / A) EQE
(%) Comparative Example 1 ET-1 10 3.5 44.7 14.2 Example 1 One 10 3.4 56.6 18 Example 2 7 10 3.26 58.8 18.8 Example 3 5 10 3.5 58.9 18.7 Example 4 9 10 3.3 58.6 19 Example 5 33 10 3.25 54.6 17.7 Example 6 35 10 3.5 59.4 19 Example 7 39 10 3.6 57.7 18.6

It can be seen that the current efficiency and EQE of Examples 1 to 7 are improved compared to Comparative Example 1.

The present invention is not necessarily limited to these embodiments, and various modifications can be made without departing from the spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (12)

The phenanthroline compound represented by Formula 1 below:
[Formula 1]

In Chemical Formula 1,
Ar ₁ and Ar ₂ are each independently selected from the group consisting of a single bond, an arylene group having 3 to 30 carbon atoms unsubstituted or substituted with phenyl, a heteroarylene group having 3 to 30 carbon atoms unsubstituted or substituted with phenyl, and a combination thereof Selected,
Ar ₃ and Ar ₄ are each independently selected from the group consisting of hydrogen, an aryl group having 3 to 30 carbon atoms unsubstituted or substituted with phenyl, a heteroaryl group having 3 to 30 carbon atoms unsubstituted or substituted with phenyl, and a combination thereof ,
L ₁ and L ₂ are each independently selected from the group consisting of a single bond, an arylene group having 3 to 30 carbon atoms unsubstituted or substituted with phenyl, and a heteroarylene group having 3 to 30 carbon atoms substituted or unsubstituted with phenyl,
Provided that when Ar ₁ and L ₁ are both single bonds, Ar ₃ is not hydrogen, and when both Ar ₂ and L ₂ are single bonds, Ar ₄ is not hydrogen;
At least one of Ar ₃ and Ar ₄ is a heteroaryl group having 3 to 30 carbon atoms unsubstituted or substituted with phenyl,
The heteroaryl group having 3 to 30 carbon atoms substituted or unsubstituted with phenyl is a pyridinyl group unsubstituted or substituted with phenyl, a pyrimidinyl group unsubstituted or substituted with phenyl, a triazinyl group unsubstituted or substituted with phenyl, and phenyl Is selected from the group consisting of an unsubstituted or unsubstituted quinolinyl group, a phenyl substituted or unsubstituted isoquinolinyl group, a phenyl substituted or unsubstituted quinazolinyl group and a phenyl substituted or unsubstituted isoquinolinyl group. . The compound of claim 1, wherein Ar ₁ and Ar ₂ are each independently a single bond, phenyl substituted or unsubstituted with phenyl, alkylphenylene, halophenylene, cyanophenylene, naphthylene, alkylnaphthylene, biphenyl Ethylene, alkylbiphenylene, pyridylene, pyrimidylene, quinolinylene, isoquinolinyl, quinoxalinylene, pyrazinylene, quinazolinylene, naphthyridinylene, openylene, furanylene, benzothiophenylene , Benzofuranylene, dibenzothiophenylene, dibenzofuranylene, fluorenylene, carbazoylene, imidazolylene, triphenylenylene, fluoroantylene and diacafluorenylene Phenanthroline compounds. delete delete The phenanthroline compound according to claim 1, wherein the heteroaryl group having 3 to 30 carbon atoms substituted or unsubstituted with phenyl is selected from the group consisting of substituents represented by the following Formulas A-1 to A-5:

The method of claim 1, wherein L ₁ and L ₂ are each independently a single bond, phenyl substituted or unsubstituted phenyl, alkylphenylene, halophenylene, cyanophenylene, naphthylene, alkylnaphthylene, biphenyl Ethylene, alkylbiphenylene, pyridylene, pyrimidylene, quinolinylene, isoquinolinyl, quinoxalinylene, pyrazinylene, quinazolinylene, naphthyridinylene, openylene, furanylene, benzothiophenylene , Benzofuranylene, dibenzothiophenylene, dibenzofuranylene, fluorenylene, carbazoylene, imidazolylene, triphenylenylene, fluoroantylene and diacafluorenylene Phenanthroline compounds. The phenanthroline compound according to claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group consisting of the following compounds:

First electrode,
A second electrode, and
At least one organic material layer positioned between the first electrode and the second electrode,
At least one layer of the organic material layer of the organic light emitting device comprising the phenanthroline compound according to any one of claims 1, 2, 5 to 7. The organic light emitting device of claim 8, wherein the organic material layer comprises at least one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes. The organic light emitting device of claim 8, wherein the organic material layer comprises at least one layer selected from the group consisting of a light emitting layer, an electron injection layer, an electron transport layer, and a layer for simultaneously injecting and transporting electrons. The organic light emitting device of claim 8, wherein the organic material layer comprises at least one charge generation layer (CGL). An image display apparatus comprising the organic light emitting element according to claim 8.

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